WO1994021734A1

WO1994021734A1 - PAINTS CONTAINING n-ALKYL-N-AZOLS AS PRESERVATIVES

Info

Publication number: WO1994021734A1
Application number: PCT/EP1994/000787
Authority: WO
Inventors: Lutz Heuer; Martin Kugler; Heinrich Schrage; Wilfried Paulus
Original assignee: Bayer Aktiengesellschaft
Priority date: 1993-03-25
Filing date: 1994-03-14
Publication date: 1994-09-29
Also published as: EP0690894A1; AU6425894A; DE4309690A1

Abstract

n-Alkyl-N-azols are used to protect paints.

Description

PAINT CONTAINING N-ALKYL-N-AZOLE AS A PRESERVATIVE.

Use of n-alkyl-N-azoles in material protection.

The application relates to the use of n-alkyl-N-azoles in the paint or in paints.

Straight-chain n-alkyl-N-azoles are known. Furthermore, it is known that these compounds are used in a protective material for disinfection (DE-A-2 442 706) or in the form of their copper salts or in mixtures for protecting wood (DE-A-3 520 394; DE-A - 3,613,232; DE-A-3,613,253; EP-A-277,556).

It is not yet known that these compounds can also be used in paints or paints.

A prerequisite for the use of the compounds for protecting paints against growth or destruction by microorganisms such as fungi, yeasts, bacteria and algae is that the compounds are not only antimicrobially active, but also colorless and in the paint by interactions with the other components of the Paints or the paint or by environmental factors such as Light, temperature, weather are not destroyed or not, e.g. by forming complexes, discolouring.

Furthermore, it is a prerequisite for the protection of paints that the protective compounds do not evaporate or be washed out of the paint. It has now surprisingly been found that from the large number of known agents with fungicidal, algicidal or bactericidal properties, the n-alkyl-N-azoles have outstanding biological activities and, moreover, the targeted properties required for painting.

The application therefore relates to the use of at least one compound of the formula (I)

in which

R represents an unbranched alkyl chain with preferably 7 to 12 carbon atoms, which is optionally interrupted by one or two sulfur or oxygen atoms,

W, X, Y, Z independently of one another represent nitrogen or the group CR ¹ , at least two standing for the group CR ¹ and in which

R ¹ ₁₀ is hydrogen or straight or branched C -C _j - represents alkyl,

for the protection of paints and paints which contain at least one of these compounds.

In the following, alkyl in the definition of R represents straight-chain alkyl, such as methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n- Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl and n-pentadecyl. Otherwise alkyl is straight-chain or branched alkyl having 1 to 10, in particular 1 to 6, carbon atoms, such as methyl, ethyl, n-, i-, s-propyl, n-, i-, s-, t-butyl.

Compounds of the formula (I) in which

R is C ₈ -C _jj alkyl, which is optionally substituted by a sulfur and / or

Oxygen atom is interrupted

W represents the groups CH or C- (C _r C ₁₀ ) -alkyl,

Z, X represents nitrogen or the group CH and

Y stands for the group CH.

Compounds of the formula (I) in which

R represents C ₉ -C _π- alkyl,

W represents the groups CH or C- (C _r C ₃ ) - alkyl,

X for nitrogen,

Y for the group CH,

Z represents nitrogen or the group CH.

The compounds are generally known or can be prepared by known methods (DE-A-2 706 838). The active compounds which can be used according to the invention have a strong microbicidal action and can be used to protect paints against attack and destruction by undesired microorganisms.

In the present context, painting is to be understood as a coating on a substrate made from paint materials. The paint may have penetrated more or less into the surface. It can consist of one or more layers and can be produced by processes such as brushing, spraying, dipping, flooding or similar processes.

The compounds to be used according to the invention are incorporated in the paints or in precursors for the preparation of the paints by customary methods, e.g. by mixing the active ingredients with the other components.

The paints according to the invention therefore contain, in addition to the fungicidal active ingredient, customary paint components in e.g. liquid, pasty or powdery form such as

- Colorants, such as pigments or dyes, preferably pigments. Examples include titanium dioxide, zinc oxide and iron oxide.

Binders, such as, for example, oxidatively drying alkyd resins, vinyl polymers and vinyl copolymers, acrylic polymers and acrylic copolymers, plastic powders, novolaks, amino resins, polyester resins, epoxy resins, silicone resins, isocyanate resins, vinyl polymers and vinyl copolymers, acrylic polymers and other acrylic copolymers are preferred, and other acrylic copolymers usable binders.

The paints may also contain the following additives Fillers such as heavy spar, calcite, dolomite and talc,

Solvents, such as alcohols, ketones, esters, glycol ethers and aliphatic and aromatic hydrocarbons,

as well as thickening and thixotropic agents, dispersing and wetting agents, drying agents, skin-preventing agents, leveling agents, anti-foaming agents, corrosion inhibitors, UV absorbers, fragrances, antistatic agents, antifreeze agents.

The following may preferably be mentioned as paints or precursors for the production of paints:

Glues and adhesives based on the well-known animal, vegetable or synthetic raw materials.

Plastic dispersions such as latex dispersions or dispersions based on other polymers.

Starch solutions, dispersions or slurries or other starch-based products such as Pressure thickener. - Slurries of other raw materials such as color pigments (e.g. iron oxide pigments,

Carbon black pigments, titanium dioxide pigments) or slurries of fillers such as kaolin or calcium carbonate.

Concrete additives, for example based on molasses or lignin sulfonates.

Bitumen emulsions. - preliminary and intermediate products of the chemical industry, e.g. in the

Dye fabric production and storage.

Inks or inks.

Dispersion paints for the painting industry.

Coats and finishes. Bacteria, fungi, yeasts, algae and slime organisms may be mentioned as microorganisms which can degrade or change the coatings. The active substances which can be used according to the invention preferably act against fungi, in particular molds, discoloring and destructive fungi (Basidiomycetes) and against mucus organisms and algae.

For example, microorganisms of the following genera may be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, like Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on the field of application, the active compounds to be used according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules.

The application concentrations of the active compounds to be used according to the invention depend on the type and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal one The amount used can be determined by test series. In general, the application concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

The effectiveness and the spectrum of activity of the active ingredients which can be used according to the invention or of the agents, precursors or very generally formulations which can be prepared therefrom can be increased if further antimicrobial compounds, fungicides, bactericides, herbicides, insecticides or other active ingredients are used to enlarge the spectrum of activity or to achieve special effects such as added protection against insects. These mixtures can have a broader spectrum of activity than the compounds according to the invention.

In many cases, synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components. Particularly favorable mix partners are e.g. the following connections:

Triazoles such as:

Amitrole, azocyclotine, BAS 480F, bitertanol, difenoconazole, fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol, imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole, paclobutrazole (4-) -conazazole-l, -conconazole-l, -cononazole-l, -conconazole-l, -conconazole-l, -conconazole-l, chlorphenyl) -2- (lH-l, 2,4-tri__zol-l-yl) -cycloheptanol, tetraconazole, triadimphone, triadimenol, triapenthenol, triflumizole, triticonazole, uniconazole and their metal salts and acid adducts. Imidazoles such as:

Imazalil, Pefurazoate, Prochlora__, Triflumizole, 2- (l-tert-Butyl) -l- (2-chlorophenyl) -3-

(l, 2,4-triazol-l-yl) propan-2-ol, thiazolecarboxanilides such as 2 ', 6'-dibromo-2-methyl-4-trifluoromethoxy ^' - trifluoromethyl-1, 3-thiazole-5- carboxanilide, 1 -imidazolyl-1 - (4 ¹ - chlorophenoxy) -3,3-dimethylbutan-2-one and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl (E) -2- [2- [6- (2-thioamidophenoxy) pyrimidine- 4-yloxy] phenyl] -3-methoxyacrylate, methyl © -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, memyl (E) -2- [ 2- [6- (2,6-difluorophenoxy) pyrimicl_n-4-yloxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] - 3-methoxyacrylate, methyl ^) - 2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylate methyl (E) - 2- [2- [3- (phenylsulfonyloxy ) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl> Q) -2- [2-phenoxyphenyl] - 3-methoxyacrylatemethyl (E) -2- [2- (3,5-dimethylbenzoyl) pyrrol-l-yl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] - .3-methoxyacrylates, methyl (E) -2- [2- (2-phenylethen-l-yl) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- (3,5-dichlorophenoxy) ) pyridin-3-yl] -3-methoxyacrylates, methyl (E) -2- (2- (3- (l, l, 2,2-tetrafluoroethoxy) phenoxy) phenyl) -3-me thoxyacrylates, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3-methoxyacrylates, methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3 - methoxyacrylate, methyl (Ε) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E) -2- [2- (3-isopropyloxy phenoxy) phenyl] - 3-methoxy acr 1 ate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-ethoxy-phenoxy ) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [ 3- (3-cyanophenoxy) phenoxy] phenyl] -3-methoxyacrylate methyl (E) -2- [2- (3-methylpyridin-2-yloxymethyl) phenyl] -3-methoxyacrylic latemethyl (E) -2- [ 2- [6- (2-methylphenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (5-bromopyridin-2-yloxymethyl) phenyl] -3-methoxyacrylate , methyl (E) -2- [2- (3- (3-iodopyridin-2-yloxy) phenoxy) phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacylatej (E), (E) methyl-2- [2- (5,6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] - 3-methoxyacrylate (E) -me_hyl-2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] - phenyl} - 3-methoxyacrylate, (E), (E) methyl-2- {2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate (E) methyl-2- {2- (6- (2-azidophenoxy ) -pyrimidin-4-yl-oxy] phenyl} 3-methoxyacrylate (E), (E) methyl-2- {2- [6-phenylpyrimidin-4-yl) methyl-oximinomethyl] phenyl} -3-methoxyacrylate, {E), (E) methyl-2- {2 - [(4-chlorophenyl) methyloximinomethyl] phenyl} -3-methoxyacrylate, (E) methyl-2- {2- [6- (2-n- propylphenoxy) - 1,3,5 -triazin-4-yloxy] phenyl} -3-methoxyacrylate, (E), (E) methyl-2- {2 - [(3-ni-phenyl) methyloximinomethyl] phenyl } -3-methoxyacrylates;

Succinate dehydrogenase inhibitors such as:

Fenfuram, furcarbanil, cyclafluramide, furmecyclox, seedvax, metsulfovax, pyrocarbolide, oxycarboxin, shirlan, mebenil (mepronil), benodanil, flutolanil (moncut);

Naphthalene derivatives such as terbinafine, naftifine, butene fame, 3-chloro-7- (2-aza-2,7,7-trimethyl-oct-3-en-5-in);

Sulfenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet; Captan, Captofol;

Benzimidazoles such as Carbendazim, Benomyl, Furathiocarb, Fuberidazole, Thiophonat-methyl, Thiabendazole or their salts;

Morpholine derivatives such as tridemorph, fenpropimorph, falimorph, dimethomorph, dodemorph, aldimorph, fenpropidine and their arylsulfonic acid salts, e.g. p-

Toluenesulfonic acid and p-dodecylphenyl sulfonic acid;

Dithiocarbamate, Cufraneb, Ferbam, Mancopper, Mancozeb, Maneb, Metam,

Metiram, Thiram Zeneb, Ziram;

Benzothiazoles such as 2-mercaptobenzothiazole; Benzamides such as 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide;

Boron compounds such as boric acid, boric acid ester, borax; Formaldehyde and formaldehyde-releasing compounds such as benzyl alcohol mono- (poly) hemiformal, oxazolidines, hexa-hydro-S-triazines, N-methylolchloroacetamide, paraformaldehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldi-_zeniumdioxy) aluminum, N- (cyclo-hexyldiazeniumdioxy) -tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one, 4,5- Trimethylene-isothiazolinone, 4,5-benzisothiazolinone, N-methylolchloroacetamide; Aldehydes such as cinnamaldehyde, formaldehyde, glutardialdehyde, β-bromocinnamaldehyde; Thiocyanates such as thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, etc; quaternary ammonium compounds such as benzyldimethyltetradecylammonium chloride, benzyldimethyldodecylammonium chloride, didecyldimethylammonium chloride; Iodine derivatives such as diiodomethyl-p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropyl methyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-triiodallyl alcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propynyl-n-butyl carbamate, 3-iodo-2-propynyl-n-hexyl carbamate, 3-iodo-2-propynyl-cyclohexyl carbamate, 3- Iodine-2-propynylphenyl carbamate;

Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlorophenol and their alkali and alkaline earth metal salts;

Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol, 2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, β-bromo-β-nitrostyrene; Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione, 1-hy droxy-4-methy l-6- (2,4,4-trimethylpentyl) -2 (1 H) pyridine;

Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate, phosphate, benzoate; Metal salts such as copper hydroxycarbonate, sodium dichromate, potassium dichromate,

Potassium chromate, copper sulfate, copper chloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

Oxides such as tributyltin oxide, Cu ₂ O, CuO, ZnO; Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates,

Tetramethylthiuram disulfide, potassium N-methyldithiocarbamate;

Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile, disodium cyano-dithioimidocarbamate;

Quinolines such as 8-hydroxyquinoline and their Cu salts;

Mucochloric acid, 5-hydroxy-2 (5H) furanone; 4,5-dichlorodithiazolinone, 4,5-benzdithiazolinone, 4,5-trimethylene dithiazolinone, 4,5-

Dichloro- (3H) -l, 2-dithiol-3-one, 3,5-dimethyl-tetr__hydro-l, 3,5-thiadiazin-2-thione,

N- (2-p-chlorobenzoylethyl) hexaminium chloride potassium N-hydroxymethyl-N'-methyldithiocarbamate,

2-oxo-2- (4-hydroxy-phenyl) acethydroximic acid chloride, phenyl- (2-chloro-cyano-vinyl) sulfone,

Phenyl- (1,2-dichloro-2-cyano-vinyl) sulfone;

Zeolites containing Ag, Zn or Cu alone or included in polymeric active substances.

Mixtures with are very particularly preferred

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metaconazole, penconazole, propiconazole, tebuconazole, methyl- (E) - methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2- {2- [6- (2-cyanophenoxy) -py-rimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4- (2,2-difluoro-1,3 -benzodioxol-4-yl) -lH-pyrrole-3-carbonitrile, butenafine, imazalil, N-methyl-isothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one, Benzisothiazolinone, N- (2-hydroxypropyl) amino-methanol, benzyl alcohol (hemi) formal, glutaraldehyde, omadine, dimethyl dicarbonate, and / or 3-iodo-2-propynyl-n-butyl carbamate. Furthermore, well-effective mixtures with the following active ingredients are also produced:

Fungicides:

Acypetacs, 2-aminobutane, Ampropylfos, anilazine, benalaxyl, Bupirimate, chinomethionat, chloroneb, chlozolinate, cymoxanil, dazomet, Diclomezine, Dichloram, diethofencarb, dimethirimol, Diocab, dithianon, dodine, Drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol, Fenitropan, Fentin acetate, Fentin Hydroxide, Ferimzone, Fluazinam, Fluromide, Flusulfamide, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane, Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Perfarurol, Nuarimol , Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quintozene, Tar Oils, Tecnazene, Thicyofen, Thiophanate-methyl, Tolclofos-methyl, Triazoxide, Trichlamine, Tricyclinezoline, Tricycolinezole, Tricyclinezoline, Tricyclazine

Insecticides:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, -l (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy-pyrazole, chlorpyrifos, Coumaphos, Demeton, Demeton-S-methyl, diazinon, dichlorvos, dimethoate , Ethoate, Ethoprophos, Etrimfos, Fenitrothion, Fenthion, Heptenophas, Parathion, Parathion-methyl, Phosalone, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Prothiofos, Sulfprofos, Triazophos and Trichlorphone;

Carbamates such as aldicarb, bendiocarb, α-2- (l-methylpropyl) phenylmethyl carbamate, butocarboxime, butoxycarboxime, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb; Organosilicon compounds, preferably dimethyl (phenyl) silylmethyl-3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or (Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as dimethyl- (9-ethoxyphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) -propyl] (dimethyl) -silanes such as (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl] dimethyl-silane, silafluofen; pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin, cycloprothrin, cyfiuthrin, Decamethrin, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2-chloro-2-trifluoromethylvinyl) cyclopropane-carboxylate, fenpropathrin, fenfluthrin, fenvalerate, flucythrinate , Flumethrin, fluvalinate, permethrin, resmethrin and tralomethrin; nitroimines and nitromethylenes such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazole-2-amine (imidacloprid ), N - [(6-chloro-3-pyridyl) methyl-] N ² -cyano-N'-methylacetamide (NI-25);

Abamectin, AC 303, 630, Acephate, Acrinathrin, Alanycarb, Aldoxycarb, Aldrin, Amitraz, Azamethiphos, Bacillus thuringiensis, Phosmet, Phosphamidon, Phosphine, Prallethrin, Propaphos, Propetamphos, Prothoate, Pyraclofos, Pyrethriproxyphid, Pyrethridafid, Pyrethridafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafid, Pyrethrinsafide, RH-7988, Rotenone, Sodium fluoride, Sodium hexafluorosilicate, Sulfotep, Sulfuryl fluoride, Tar Oils, Teflubenzuron, Tefluthrin, Temephos, Terbufos, Tetrachlorvinphos, Tetramethrin, O-2-tert.-Butyl-pyrimidin-5-yl-o-isopropyl -phosphorothiate, Thiocyclam, Thiofanox, Thiometon, Tralomethrin, Triflumuron, Trimethacarb, Vamidothion, VerticiUium Lacanii, XMC, Xylylcarb, Benfuracarb, Bensultap, Bifenthrin, Bioallethrin, MERbioomeretophin, Bromine-Bophentophos, Ethyl Biosulphophos, Ethyl Biosulphos, Ethyl Biosulphosphate Calcium polysulfide, carbophenothione, cartap, quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin, alpha-cypermethrin, cyopheno thrin, Cyromazine, Dazomet, DDT, Demeton-S-methylsulphone, Diafenthiuron, Dialifos, Dicrotophos, Diflubenzuron, Dinoseb, Deoxabenzofos, Diaxacarb, Disulfoton, DNOC, Empenthrin, Endosulfan, EPN, Esfenvalcarbx, Feni Fensulfothione, fipronil, flucycloxuron, flufenprox, flufenoxuron, Fonofos, Formetanate, Formothion, Fosmethilan, Furathiocarb, Heptachlor, Hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Metathamamusamos, Malathionphosphate, Chloride , anisopliae, Methacrifos, Methami dophos, Methidathion, Methiocarb, Methoprene, Methoxychlor, Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Petroleum Phophlorophenol; Phonachlorophenol;

Moiluscicide: fentin acetates, metaldehydes, methiocarb. Niclosamide, thiodicarb, trimethacarb.

Algicide:

Coppersulfate, dichlororphen, Endothal, Fentinacetate, Quinoclamine.

Herbicides: acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam atrazine, aziptrotryne, benazolin, benfluralin, benfuresate, bensulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron, benzenesulfuron borax, dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron, difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid, dinitramine, dinoseb, dinoseb, dinoseb acetate, dinosebomobomilomomolomomom butachlor, butamifos, fuenachlor, butralin, butylates, carbetamides, CGA

184927, chloromethoxyfen, chloramben, chlorbromuron, chlorobutam, chlorofurenol, chloridazon, chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin, chlorotoluron, chloroxuron, chlorprepham, clorosulfuron, chlorthal, chlorthinomidone, cinethonidomid, cinethonidomidomid, cinethonidomidomidomethomidomidone, cinethonomethane, chlorthinomidone, cinethonomethane, chlorthinomidone, cinchloromethane, chlorthinomidone, cinchloromethanone , dinoseb acetate, dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788, DPX-E96361, DSMA, eglinazine, endothal, EPTC, esproca b, ethalfluralin, ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazop-, fluazifop P, fluchloralin, flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol, fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetrynil, dicamba, dichlor isoproturon, isouron, isoxaben, isoxapyrifop, lactofen, lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor, methabenzthiazdronate, methylazole methylthiuron, methazethole, methyl, methabenzthiazuron, methyl metobromuron, fomosafen, fosamine, furyloxyfen, glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz, imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, propyzamide, prosulfocab, pyrazolynate, pyrazolsulfclora, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxine, pyrutoxin c, quinmerac, quinocloamine, quizalofop, quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY 1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor, metoxuron, metribzin, metsulfuron, moninolinur, moninolinur, moninolinur , MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron, nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen, paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor, petroleum oils, phenmedulfineuron, phenmedipilone, phenmedipilone proglinazine, propmeton, prometryn, propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil, tioclorim, tralkoxydim, tri-allic, trisulfuron, triasulfuron, triasulfuron C4874 vernolate, propanil, propaquizafop, propazine, propham.

The weight ratios of the active ingredients in these active ingredient combinations can be varied within relatively large ranges. The active compound combinations preferably contain the active compound in an amount of 0.1 to 99.9%, in particular 1 to 75%, particularly preferably 5 to 50%, the rest being filled 100% by one or more of the above-mentioned mixing partners.

The microbicidal agents or concentrates used to protect the industrial materials contain the active ingredient or combination of active ingredients in a concentration of 0.01 and 95% by weight, in particular 0.1 to 60% by weight.

Other active substances which may also be used are algicides such as diuron, molluscicides, active substances known as "sea animals", which relate to e.g. Place ship floor paints.

The active substances or agents according to the invention advantageously make it possible to replace the microbicidal agents available to date with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

The following examples serve to illustrate the invention. The invention is not limited to the examples.

MANUFACTURING EXAMPLES

example 1

2 mol of 2-ethylimidazole and 2.2 mol of n-dodecyl bromide are heated to 130 ° C. for 30 minutes and then 3.2 mol of NaOH are added. The reaction mixture is then heated to 150 ° C. for a further 2 hours. The inorganic residue is filtered off and washed with benzene. The combined filtrates are distilled. 468 g of l-dodecyl-2-ethylimidazole pass between 118 and 122 ° C. and 0.5 Torr.

The connections listed in the table below are produced in an analogous manner:

Type A Type B Type C Ty D

Application example

A. To demonstrate the activity against fungi, the minimum inhibitory concentrations (MIC) of agents according to the invention are determined:

An agar which is produced using malt extract is mixed with active substances according to the invention in concentrations of 0.1 mg / 1 to

5000 mg / 1 added. After the agar solidifies, it is contaminated with pure cultures of the test organisms listed in Table 1. After 2 weeks of storage at 28 ° C and 60 to 70% relative humidity, the MIC is determined. MIC is the lowest concentration of active ingredient at which no growth occurs due to the type of microbe used, it is shown in Table 2 below.

Table 2 (comparison) MICs when fungi act on compounds of the invention

B. Testing the mold resistance of paints

The substance to be tested for its fungicidal activity is incorporated in the desired concentration in the (dispersion) color using a dissolver. The paint is then spread on both sides on a suitable surface.

In order to obtain practical results, some of the test specimens are leached with running water (24 h; 20 ° C) before the test for mold resistance.

The test specimens prepared in this way are placed on an agar culture medium. Test specimens and culture medium are contaminated with fungal spores. After 1 to 3 weeks of storage at 29 ± 1 ° C and 80-90% rel. Humidity is sampled. The paint is permanently mold-resistant if the test specimen remains free of fungi or if at most a slight edge infestation can be seen.

Fungus spores of the following nine molds, which are known as paint destroyers or are frequently encountered on paints, are used for contamination:

1. Alternaria tenuis

2. Aspergillus flavus

3. Aspergillus niger

4. Aspergillus ustus 5. Cladosporium herbarum

6. Paecilomyces variotii

7. Penicillium citrinum

8. Aureobasidium pullulans

9. Stachybotrys atra Corda -.

Active substance concentrations at which the paint sample remains free of fungi (concentration based on the solids content of the emulsion paint)

Claims

1. Use of at least one compound of the formula (I)

in which

R ^{1 is} hydrogen or straight-chain or branched C _j -C ₁₀ -

Alkyl stands,

to protect paints.

2. Use according to claim 1, characterized in that in the connections of the formula (I)

R represents an unbranched alkyl chain with 7 to 12 carbon atoms, which is optionally interrupted by one or two sulfur and / or oxygen atoms.

3. Use according to claim 1, characterized in that in the connections of the formula (I)

R represents C ₈ -C _π- alkyl, which is optionally interrupted by a sulfur and / or oxygen atom,

W represents the group CH or C (C _r C ₁₀ alkyl),

Z, X independently of one another represent nitrogen or the group CH and

Y stands for the group CH.

4. Use according to claim 1, characterized in that in the connections of the formula (I)

R is C ₈ -C ^ alkyl,

W represents the groups CH or C (C _r C ₃ alkyl),

X for nitrogen,

Y for the group CH,

Z represents nitrogen or the group CH.

5. Paints containing at least one in addition to paint components

A compound of formula (I) according to claim 1.

6. Emulsion paints containing at least one compound of the formula (I)

Claim 1.