CA2238033A1 - Water-based solvant-free and emulsifier-free microbicidal combination of active substances - Google Patents

Abstract

Described are microbicidal, optionally solvent-free and emulsifier-free activesubstance combinations or agents made up of prior art azole fungicides, a nitromethylene-type insecticide and quaternary ammonium compounds, plus the use of such combinations in the protection of equipment and materials.

Description

~ ~ ~ CA 02238033 1998-05-19 ... . .
FILE~ PIN 1~ THIS AI~E!~ D
Le A 31 346 - Forei~n countries/LIN/bo/S-P r~ I I RANSLATIVN

Water-based, solvent- and emulsifier-free microbicidal active co,nl~ound combination The present invention relates to new, in particular aqueous and optionally organic solvent- and emulsifier-free microbicidal active compound combinations comprising known azole fungicides, ~lu~e~ y ammonium fungicides, and an in~ecticicle from the 5 class of the nitromethylenes.

It is known that imitl~7~1e fungicides and triazole fungicides, such as, for example, a-[2-(4-chlo~ ellyl)-ethyl]-a-(1,1-dimethylethyl)-1-H-1,2,4-triazole-1-ethanol (tebuco-nazole), 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,3-triazol-1-yl)-propan-2-ol andl - [[2 -(2,4-dichlorophenyl)-4-n-propyl- 1,3 -dioxolan-2 -yl] -methyl] - 1 -H- 1,2,4-triazole 10 (propiconazole), can be used as such or in the form of their salts for pl~le~ g plants and seeds (co~ , for example, EP-A 0,040,345 and EP-~ 0,052,424).

It is furthermore known that these compounds are also suitable for use in the preservation of m~t~ri~l~ for combating microbes which destroy m~teri~l~ or discolour m~ten~l~ (compare, for example, DE-OS (German Published Specification) 3,621,494 and US 4,079,062).

However, the azole fungicides, such as the tebuconazole mentioned, have gaps in their action on some germs relevant to the pleselv~Lion of m~teri~l~, such as, for example, Trichoderma spec.

Because of the often low water-solubility of azoles, their use in some fields of20 application, such as, for example, leather, water-based wood ~l~ s~l v~ives, disinfection, cooling water treatment, paper industry, metal proc~c~ing and industrial preservation of water-co..l;~ products, is furthermore limited or impossible.

The agonists and antagonists of the nico~ ic acet,vlcholine rc;c~lols are compounds which are known from the following publications:

25 European Published Specifications Nos. 664 081, 464 830, 428 941, 425 978, 386 565, -~ ~ CA 02238033 1998-0~-19 .~ , Le A 31 346 - Forei~n countries 383 091, 375 907, 364 844, 315 826, 259 738, 254 859, 235 725, 212 600, 192 060,163 855, 154 178, 136 686, 303 570, 302 833, 306 696, 189 972, 455 000, 135 956,471 372, 302 389;

German Published Specifications Nos. 3 639 877, 3 712 307;

J~p~n~se Published Specifications Nos. 03 220 176, 02 207 083, 63 307 857, 63 287 764, 03 246 283, 04 9371, 03 279 359, 03 255 072;

US-Patents Nos. 5 034 524, 4 948 798, 4 918 086, 5 039 686, 5 034 404, PCT Applications Nos. WO 91/17 659, 91/4965;

French Application No. 2 611 114;

Br~7.ili~n Application No. 88 03 621.

The generic formulae and definitions described in these publications and also the individual compounds described therein are expressly incorporated by lerer~llce.
Some of these compounds are collated under the term nitromethylenes and related compounds.

These compounds can preferably be ~ ;;~d under ~e general formula (TI) (A) 8 (II) X--E
in which , CA 02238033 1998-05-19 Le A 31 346 - Forei~n countries R represents hydrogen or optionally substituted radicals acyl, alkyl, aryl, aralkyl, heteroaryl or heteroarylalkyl;

A represents a monofimctional group from the series hydrogen, acyl, alkyl and aryl or r~l~s~l~ a bifunctional group which is linked with the radical Z;

5 E represents an electron-attracting radical;

X represents the radicals -CH= or =N-, where the radical -CH= can be linked in place of a H atom to the radical Z;

Z represents a monofunctional group from the series alkyl, -O-R, -S-R and --N\
R

or represents a bifunctional group which is linked to the radical A or to the radical X.

Particularly pl~;relled compounds of the formula (II) are those in which the radicals are defined as follows:

E~ represents hydrogen and represents optionally substituted radicals from the series acyl, alkyl, aryl, aralkyl, heteroaryl and heteroarylalkyl.

Acyl radicals that may be mentioned are formyl, alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl and (alkyl-)-(aryl-~-phosphoryl, which may in turnbe substituted.

Alkyl that may be mentioned is C,-C10-alkyl, especially Cl-C4-alkyl, specifically methyl, ethyl, i-propyl, sec- or t-butyl, which may in turn be substituted.

'~ CA 02238033 1998-0~-19 .
Le A 31 346 - Forei~n countries Aryl that may be mentioned is phenyl or naphthyl, especially phenyl.

Aralkyl that may be mentioned is phenylmethyl or phenethyl.

Heteroaryl that may be mentioned is heteroaryl having up to 10 ring atoms and N, O, S, especially N, has heteroatoms. Specific mention may be made of S thiophenyl, furyl, thiazolyl, imidazolyl, pyridyl or benzothiazolyl.

Heteroarylalkyl that may be mentioned is heteroarylmethyl or heteroarylethyl having up to 6 ring atoms and N, O, S, especially N, as heteroatoms.

Examples of ~l~;r~ ;d el-bstit~lent~ that may be cited are:

Alkyl having preferably 1 to 4, especially 1 or 2 carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; alkoxy having preferably l to 4, especially 1 or 2 carbon atoms, such as methoxy, ethoxy, n- and i-propyloxy - and n-, i- and t-butyloxy; alkylthio having preferably 1 to 4, especially 1 or 2 carbon atoms, such as methylthio, ethylthio, n- and i-pr~yl~.~o and n-, i- and t-butylthio, halogenoalkyl having preferably 1 to 4, especially 1 or 2 carbon atoms and preferably 1 to 5, especially 1 to 3 halogen atoms, the halogen atoms being identical or different and being preferably fluorine, chlorine or bromine,especially fluorine, such as trifluoromethyl, hydroxyl; halogen, preferably fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; cyano; nitro; arnino; monoalkyl- and diaL~ylamino having preferably 1 to 4, especially 1 or 2 carbon atoms per aLkyl group, such as methyla~nino, methylethylamino, n- and i-propylamino and methyl-n-butylamino; carboxyl;
carboalkoxy having preferably 2 to 4, especially 2 or 3 carbon atoms, such as carbomethoxy and carboethoxy; sulpho (-SO3H); alkylsulphonyl having preferably 1 to 4, especially 1 or 2 carbon atoms, such as methylsulphonyl and ethylsulphonyl; arylsulphonyl having preferably 6 or 10 aryl carbon atoms, such as phenylsulphonyl, and heteroarylamino and heteroarylalkylamino, such as chloropyridylamino and chloropyridylmethylamino.

Le A 31 346 - Forei~n countries A represents hydrogen and represents optionally substituted radicals from the series acyl, aLkyl and aryl which preferably have the me~ningC given above; A
additionally leplese~ a bifunctional group. Mention may be made of optionally sul~ uL~d alkylene having 1 to 4, especially 1 to 2 carbon atoms, substituents which may be mentioned being the substituents listed above.

A and Z can, together with the atoms to which they are ~ r.1lf ~1, form a saturated or unsaturated heterocyclic ring. The heterocyclic ring can contain a further 1 or 2 identical or different heteroatoms and/or hetero-groups. Hett;ro~Lolns are preferably oxygen, sulphur or nitrogen and hetero- groups are preferably N-alkyl, the alkyl of the N-alkyl group preferably co,.~ g 1 to 4, especially 1 or 2 carbon atoms. ALkyl that may be mentioned is methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ring contains S to 7, ~l-,fcldl~ly 5 or 6 ring members. Examples that may be mentioned of the heterocyclic ring are pyrrolidine, pipr~icline, piperazine, h~Y~n~ethyleneimine, morpholine and N-1 5 methylpiperazine.

E r~lt;sell~ an electron-withdrawing radical, it being possible in particular tomention NO2, CN, halogenoaL~cylcarbonyl such as l,S-halogeno-CI-C4-carbonyl, especially COCF2.

X lel~resell~ -CH= or -N=.

20 Z represents optionally substituted radicals aLkyl, -OR, -SR and -NRE~, R and the substituents preferably having the mt~.~ninp given above.

Z can, together with the atom to which it is ~ rh~d and with the radical -~ CA 02238033 1998-05-19 Le A 31 346 - Forei~n countTies form in place of X a saturated or lln~tllr~ted heterocyclic ring. The heterocyclic ring can contain a fi~ther 1 or 2 identical or dirrerel~t heteroatoms and/or hetero-groups. Heteroatoms are preferably oxygen, sulphur or nitrogen and hetero- groups are preferably N-allyl, the alkyl or the N-alkyl group preferablyS co.. l~i.. i.. g 1 to 4, especially l or 2 carbon atoms. ALkyls that may be mentioned are methyl, ethyl, n- and i-propyl and n-, i- and t-butyl. The heterocyclic ringcontains S to 7, preferably 5 or 6 ring members. Examples that may be mentioned of the heterocyclic ring are pyrrolidine, piperidine, pipera7ine~
he~methyleneimin~, morpholine and N- mc;lllyl~i~c,d~le.

10 The agonists and antagonists of the nicotinergic acetylcholine receptors are, with particular preference, compounds of the formula (II) Subst R represents ~(CH2)n or SUbst ~3~(CH2)n where n represents l or 2, 15 Subst. represents one of the abovementioned subst~t ll-nt~, in particular l~le3c~
halogen, especially represents chlorine, and A, Z, X and E have the m~nin~ givenabove.

Very particularly p,~r~"ed agonists and antagonists of the nicotinergic acetylcholine receptors are compounds of the following formulae:

~ Cl ~ CH2 N ~ N(CH3)2 (lla) ~NO2 (llb) N--NO2 ~e A 31 346 - Forei~n count~es Cl~;3N~NH Cl~ ICH
CH N
(llc) \No2 (lld) CN

C143CH--N--C--CH ~NCH~

N 1 I Cl ~3CH2--N ~ N--CH3 (lle) CN (lifl N--NO2 C H
C1~3CH2 N--C--NHCH3 N
(119) N ~

especially the compound of the formula ~CH2--NyNH
(llh) N~

These compounds too are often of low solubility in water and can only be used to a lirnited extent, if at all, in water-c~ products.

Quaternary ammonium salts have been known for a long time as microbicides havinga broad action and are used, for example, in disinfection and preservation of textilt~c-10 Although these active compounds are usually readily water-soluble, they tend to foam severely at the use concentrations, which causes trouble in many fields of use.
Furthermore, because of their cationic properties, they can react with anionic components, such as soaps, s~ ctS-nt~ and the like. This can adversely infl~ence their '. CA 02238033 1998-05-19 .
I e A 31 346 - Forei~n countries profile of properties, or they may become deactivated. It ls furthermore known that ~lu~ .y ammonium salts can easily be deactivated by the presence of protein and dirt.

For many uses in the practice of preservation of m~teri~l~ it is desirable to employ the S active compounds in liquid fo~ tions which are free from organic solvents or in which the corresponding solvent content is drastically re~ ce-l Water-insoluble solvents are incomp~tihle with aqueous products such as leather liquors, emulsion paints, cooling and process water and ~ infectants.

The users are often also not equipped to handle products in the forrn of solutions in 10 organic solvents, since particular devices, associated with high investment costs, are n,~ce~ry for application from the solvent and for recovery thereof, which is essential to avoid ecological problems.

Water-soluble solvents would in principle be suitable as solubilising agents in aqueous systems. However, if they enter the waste water, they can cause ecological problems.
15 Furthermore, solvents can manifest themselves adversely in the products to be preserved.

Another possibility of solubilisation for the ~.~pdlaLion of water-based active compound formulations is to use ~mnl~ifiers. In the case of highly water-insoluble compounds, such as azoles, large amounts of em~ ifier are as a rule needed for this, which is to be 20 avoided for ecological reasons. The activity of the microbicidal active compound can likewise be severely impaired by the use of em~ ifiers. The usefulness for certain systems may also be limite-l The object of the invention was therefore to provide new, preferably water-based, solvent- and em~ ifier-free microbicidal active compound forrnulations based on azole 25 fungicides and insecticides from the class of the nitromethylenes, which can be diluted easily with water and then give storage-stable solutions for use.

'' CA 02238033 1998-0~-19 I~e A 31 346 - Forei~n countries g It has now been found, surprisingly, that stable aqueous solutions or emulsions which have a particularly high microbicidal and insecticidal activity can be prepared by combination of at least one azole fungicide, preferably - 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazo-1-yl)-2-butanones (tri~1imefon) - ,B-(4-chlorophenoxy3-a-( 1,1 -dimethyl-ethyl)- 1 H- 1 ,2,4-triazole- 1 -ethanol imenol) - :~ a-[2-(4-chlor~h~llyl)-ethyl]-a-(1,1-dimethylethyl)-lH-1,2,4-triazole-1-ethanol (tebuconazole) - (RS)-2-(2,4-dichlorophenyl)-1-(lH-1,2,4-triazol-1-yl)-hexan-2-ol (hexaconazole) - l-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imi~1~7nle (prochloraz) - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol - 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolon-2-yl]-methyl]-lH-1,2,4-triazole ~ (propionazole) - 1 -[2-(2,4-dichlorophenyl)- 1,3 -dioxolon-2-yl-methyl]- 1 H- 1 ,2,4-triazole (azaconazole) - (R~, R~)-a-(4-chlorophenyl)-a-(1-cyclopropylethyl)lH-1,2,4-triazole-1-ethanol(cyproconazole) the isomers and isomer ~ eS of the most diverse compositions also being included in the cases where the compounds have asymmetric carbon atoms;

especially preferably + a-[2-(4-chlorophenyl)-ethyl]-a-( 1,1 -dimethylethyl)- 1 H- 1,2,4-triazole-l-ethanol (tebuconazole) and/or propiconazole 25 and at least one insecticide from the class of nitromethylenes, preferably of the formulae (IIa) to (IIh), in particular the compound (Ih), and at least one quaternary arnmonium fungicide, preferably of the formula (III) '- CA 02238033 1998-05-19 Le A 31 346 - Forei~n countries R2 N R3 X (III) in which R2, R3 and R4 are identical or di~e.~ and in each case represent l-n~llhstit~lte~l or sllbstihlterl shraight-chain or br~nche~1 sahurated or u~aLu.&led alkyl groups S having 1 to 20 carbon atoms, alkylaryl and araLtcyl groups having S to 10 carbon atoms in the aryl part and 1 to 20 carbon atoms in the alkyl part or arylgroups having S to 10 carbon atoms, and optionally mono-or polyaLkoxylated derivatives hereof; possible sllbstihlents being halogen, C,-C4-aL~yl and C,-C4-alkoxy, and wherein 2 or 3 radicals Rl to R4 on the qll~t~ ry centre, optionally with further hetero atoms, can form a s~hlr~te-1 or lln~hl~te~l 5-, 6-or 7-membered (heterocyclic) ring and X represents an anion which promotes water-solubility, such as, for example, halide, sulphate, alkylsulphonate or optionally substituted arylsulphonate.

Such aqueous formulations avoid the abovementioned ecological and use-related 15 disadvantages of solvent-based or çmlll~ifier-mefli~te-l formlll~tions and in this respect are a useful enrichment of the prior art.

Qll~t~ ammonium compounds which may be mentioned as plert;ll. d are arnmonium salts such as - Cl2-C,4-alkyl-benzyl-dimethylammonium chloride 20 - trimethyl-coconut-amrnonium chloride - didecyldimethylarnmonium chloride.

Particular pl~rerellce is given to didecyldimethylammonium chloride (DDAC).

'' CA 02238033 1998-0~-19 Le ~ 31 346 - Forei~n countries Very particular plt;rel~.,ce is given to a combination of tebuconazole and/or propiconazole and imidacloprid and didecyldimethylammonium chloride.

The proportions by weight of the active compounds in the active-compound combinations can be varied within relatively wide ranges. They are in general 5 dependent on the field of use ar d on the particular active compounds employed. These proportions by weight can, however, readily be ~let~rmin~l in test series simply by mixing the components.

The proportion by weight of qll~ttorn~ry ammonium fungicide to azole fungicide to the insecticide is preferably from 400;20:1 to S0:10:1.

10 To prepare aqueous formlll~1iQn~, the active compounds are incorporated individually or as an active compound combination, for example in the form of powders, ~r~mlle~, pastes or con~ e-l solutions, suspensions or emulsions, into water by simple mixing, and are then present in the form of an aqueous suspension, solution or emulsion.

15 The aqueous solutions or emulsions preferably contain more than 20% by weight, in particular more ~an 40% by weight of water and can be diluted wi~ water as desired to the use concentration. It is of course also possible for the active compounds alone or active compound combin~tioIl~ in the form of concentrates, solutions, suspensions, emulsions, powders, granules or pastes to be incorporated directly in the amounts 20 required for use, for example by stirring them into the composition for application.

.
The microbicidal agents contain the active compound combination in a concentration of 0.001 to 95% by weight, in particular 0.01 to 60% by weight, and in addition optionally 0.001 to 30% by weight, in particular 0.1 to 20% by weight, especially O.OS
- 10% by weight, of a suitable additional fungicide, insecticide or an additional active 25 compound.

The active compound combinations or agents according to the invention have a potent Le A 31 346 - Forei~n countries action against microorg~ni~m.~. They are used in the preservation of m~t~ri~ls for preserving industrial materials; they are active above all against moulds, wood-discolouring and wood-destroying fungi and bacteria and against yeasts, algae and slime org~ni~m~. The following genera of microorg~ni.cm~ may be mentioned as 5 examples - but without limitation:

Altern~ri~, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger and Aspergillus terreus, Aureobasidium, such as Aureobasidium pullulans, Ch~lo...;u such as Ch~tomillm globosum, Cladosporium, such as Cladospo~ ba~
Coniophora, such as Coniophora puteana, Gliocl~ m, such as Gliocl~dillm virens, 10 T.~ntiml~, such as Llontinu~ tigrinus, Paecilomyces, such as Paecilomyces varioti, Penicillium, such as Penicillium brevicaule, Penicillium ~ cllm and Penicilliurnpinophilum, Polyporus, such as Polyporus versicolor, Sclerophoma, such as Sclerophoma pityophila, Streptoverticillium, such as Streptoverticillium reticulum, Trichoderma, such as Trichoderma viride and Trichophyton, such as Trichophyton 15 ment~. upllyles;

Escherichia, such as Escherichia coli, Pseudomonas, such as Pse~l~lomonas areuginosa, and Staphylococcus, such as Staphylococcus aureus; and ~n-1icl~, such as Candida albicans.

The novel active compound combinations are particularly and olltct~ndingly suitable for 20 pl~,lecli~lg industrial m~t~ri~l~, especially wood, also against infeststion by wood-destroying insects, for example 1. Beetles Hylotrupes bajulus, Chlorophorus pilosis, Anabium pull~ ll, Xestobiurn rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus 25 br lnnell~, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate CA 02238033 1998-0~-19 Le A 31 346 - Forei~n countries monachus, Bostrychus capucins, Heterobo~ hus brunneus, Sinoxylon spec. Dinoderus mimlh1~

2. D~lllla~l~ld Sirex juvencus, Urocerus gigas, Urocerus gigas t7~i ml~, Urocerus augur 5 3. Termites Kalotermes flavicollis, Cryptotermes brevis, Heteroterrnes indicola, Reticulitermes flavipes, Reticuliterrnes santonensis, Retic~llit~rm~s lucilugus, Mastotermes darwiniensis, Zootermopsis nev~ n~i~, Cc,~,lolelll,es fofmos~nll~

The active compound combinations according to the invention can generally be 10 incorporated into all wood preservatives or wood pl~selv~ e formulations, forexample by mixing the active compounds with solvent or diluent, ~mnl~ifier, dispersant - and/or binder or fixative, water repellant, optionally sicatives and UV stabilizers and, if desired, dyes and pigrnents and other processing auxiliaries, or as additive to any other wood preservative formlll~tions.

15 The solvent and/or diluent used is an organic-ch~mi-~l solvent or solvent lni~lule and/or an oily or oil-like organic-chemical solvent or solvent mixture of low volatility, and/or a polar organic-chemical solvent or solvent mixture and/or water and at least one ~m~ ifier and/or w~ling agent, or is composed thereof.

Organic-ch~mic~l solvents which are preferably employed are those of ready or 20 moderate volatility.

Some of the readily or moderately volatile organic-chemical solvents can be replaced by organic oily or oil-like solvents of low volatility, provided that the insecticide/fungicide mixture is emulsifiable or soluble in this solvent mixture.

'- CA 02238033 1998-0~-19 .
Le A 31 346 - Forei~n countries In one preferred embodiment, aliphatic organic-chemical solvents co~ hydroxyl and/or ester and/or e~er groups are employed, for example alcohols, glycol ethers, esters or the like.

Organic-chemical binders which are used within the scope of the present invention are S the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or dissolved or dispersed or emllleified in the organic-chemical solvents employed, and in particular are binders cornposed of or comprising an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycon~ene~tion or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic 10 resin, hydrocarbon resin, such as indene-cou,ll~o,le resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as binder can be employed in the form of an emulsion, dispersion or solution. Other binders which can be used are bitumen or bituminous - 15 sllkst~nces in amounts of up to 10% by weight. In addition it is possible to employ conventional dyes, pigmente, water repellants, odour-m~ekinP; agents, inhibitors or anticorrosion agents and the like.

In accordance with the invention, at least one acrylate resin or modified acrylate resin and/or a drying alkyl resin is preferably present as organic-chemical binder in the 20 composition or in the conc.ontr~te Some or all of the abovementioned binder can be replaced by a fixative (llli;~Lul~,) or a plasticizer (nli~ ). These additives are intended to prevent vol~tili7~tion of the active compounds and cryst~ 7~tion or ~.eci~ lion. They preferably replace from 0.01 to30% of the binder (based on 100% of the binder employed).

25 The plastici_ers hail from the chemical classes of the phthalic esters, such as dibutyl, dioctyl or benzyl butyl phth~l~te7 phosphoric esters, such as tributyl phosphate, adipic esters, such as di-(2-ethylhexyl) ~.lip~t~ stearates, such as butyl stearate or amyl '' CA 02238033 1998-05-19 Le A 31 346 - Forei~n countries stearate, oleates, such as butyl oleate, glycerol ethers, or glycol ethers of relatively high molecular weight, glycerol esters and p-tolueneslllrh-~nic esters.

Chemically speaking, r~ es are based on polyvinyl alkyl ethers, for example polyvinyl methyl ether, or on ketones, such as benzophenone, ethylenebe~ phenone, S ~mines, for example alkanol~min~ such as monoethanolamine, or ~mmoni~

In accordance with the invention, infillctn~l m~tlori~l~ are non-living m~t~ri~l~ which have been prepared for use in industry. For example, in(11letri~1 m~teri~l~ which are int~ntle~l to be plvle-;Led by active compounds according to the invention from microbial alteration or destruction can be adhesives, sizes, paper and board, teYtil~s, 10 leather, wood, coating compositions and plastics articles, cooling lubricants arld other m~teri~l~ which can be infested with, or destroyed by, microor~ni~m~ Within the scope of the m~tPri~l~ to be protected it is also possible to mention parts of production plants, for example cooling-water circuits, which may be ""l~a~ed by the multiplication of microorg~ni~m~ Preferred in~ tn~l m~teri~l~ within the context of the invention are 15 adhesives, sizes, papers and boards, leather, wood, coating compositions, cooling lubricants, aqueous hydraulic fluids and cooling circuits.

The novel active compound combinations, compositions and/or concentrates are preferably employed for protecting wood and wooden m~t~ri~l~ against microorg~ni~m~, for example against wood-destroying or wood-discolouring fungi, 20 especially in tropical wood preservation.

Wood which can be protected by the active compound ~ e according to the invention, or compositions comprising the active compound ll~ e, is to be lln(1er~tQod as meaning, for example: structural timber, wooden bearns, railway sleepers, - bridge components, jetties, wooden vehicles, boxes, pallets, cont~iners, telephone poles, 25 wood pslnelling, wooden windows and doors, plywood, particle board, joinery or timber products which are used, quite generally, in housebuilding or in construction joinery.
.
Particularly effective wood ~,~;st;,~/~lion is obtained by means of large-scale Le A 31 346 - Forei~n countr~es impregnation processes, for example vacuum, double-vacuum or pless~e processes.

The amount of active compound combinations employed depends on the nature and the incidence of the microor n~ni~m~ of the gerrn count, the insects and on the medium.
The optimum amount to be employed during use can be ~1etPrmined in each case by S test series. In general, however, it is sufficient to employ 0.001 to 20% by weight, preferably 0.05 to 10% by weight of the active compound mi~ul~s, based on the m~tçri~1 to be preserved.

The insecticidal compositions or concenL.dl~s used for protecting wood and wooden m~t~ri~1~ comprise the active compound combination in a concentration of from 0.001 to 95% by weight, in particular from 0.001 to 60% by weight.

The new active compound combinations can be used as such or in the form of concçntr~tes or generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.

A suitable solvent and/or diluent is preferably water, alone or mixed with one or more 15 of the abovementioned solvents or ~ lPnt~, Pn~ ifiPr~ and dispersants.

The activity and the action s~e~;L,u,ll of the active compound combinations according to the invention or the agents, con.~ç..l.dLes or quite generally formulations which can be prepared theleLolll is increased, if a~pl~liate, if other antimicrobially active compounds, fungicides, insecticides or other active compounds are added to increase 20 the active compound spectrum or achieve particular effects, such as, for example, additional protection against insects. In many cases, additional synergisms are then also to be observed. Particularly favourable mixing partners are, for example, the following compounds:

sulphenamides, such as dichlofluanid (Euparen), tolylfluanid (Methyleul,~Lell), folpet or 25 fluorfolpet; benzimidazoles (if al!plopliate in the form of their salts), such as carbendazim (MBC), benomyl, fu~çricl~701e and thiabendazole; thiocyanates, such as '' CA 02238033 1998-05-19 Le A 31 346 - Forei~n countries thiocyanatomethylthiobenzothi~ole (TCMTB) and methylene bisthiocyanate (MBT);
morpholine derivatives, such as C,l-C,4-4-aLkyl-2,6-dimethylmorpholine homologues (tridemorph), (~)-cis4-[3-tert.-butylphenyl)-2-meLhylpro~yl]-2,6-dimethylmorpholine (fc~ opi,norph) and falimorph; phenols, such ~ o-phenylphenol, halogenated cresols, 5 tribromophenol, tetrachlorophenol, pentachlorophenol and 3-methyl-4-chlorophenol;
dichlorophen; iodo~,lop~syl derivatives, such ~ iodoplop;~yl butylcarbamate ~PBC), -chlorophellylrollllal, phenylc~l ~ te, hexylcarbamate and cyclohexylc~l,~~ e;
isothiazolinones, such as N-methylisothi~olin-3-one, 5-chloro-N-methylisothi~olin-3-one, 4,5-dichloro-N-octylisothiazolin-3-one and N-octylisothiazolin-3-one (octhilinc ne?;
10 pyridines, such as 1-hydroxy-2-pyrid*nethione (and the* Na, ~e, Mn and Zn salts) tetrachloro-4-methyl-sulphonyl~y~idine and tetrachloro-4-methyl-sulphonyl~yridine;
metal soaps, such as the naphth~n~te, octoate, 2-ethylh~.Y~ncate, olete, phosphate, benzoate and oxide of tin, copper or zinc; zinc salts of diaLkyldithioc~l?~ t~s;tetramethyldiuram disulphite (TMTD); 2,4,5,6-tetrachloroisophthalonitrile 15 (chlorothalonil); bt;~l~iazoles, such as 2-mercaptobenzothiazole; thiazolyl-ben7.imitl~7~1e; quinolines, such ~ ~-hy~v~yquinoline; benzyl alcohol ~ mono(poly)hemiformal; and tris-N-(cyclohexyldia7eniumdioxy)-~l-m~inium and N-(cyclohexyldiaGeniu,lldioxy)-tributyltin.

Insecticides which are preferably added are:

20 phosphoric acid esters, such as azinphos-ethyl, azinphos-methyl, 1-(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxy-pyrazole (IIA-230), chlol~yliros, co-lm~phos, demeton, demeton-S-methyl, Diazinon, dichlorvos, dimetho~t~7 ethoprophos, etrimfos, fc~ olllion, fention, heptenophos, parathion, parathion-methyl, phosalone, phoxion, pirimiphos ethyl, ~ .hos methyl, profenofos, prothiofos, sulprofos, triazophos and 25 trichlorophone;

carb~m~te.s, such as aldicarb, bendiocarb, BPMC (2-(1-melllyll,r~,~yl)phenyl methylcarbamate), butocarboxim, butoxycarboxim, call.~uyl, carbofuran, carbosulphan, cloethocarb, isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

Le A 31 346 - Forei~n countries pyletl~oids, such as allethrin, alphamethrin, bioresmethrin~ byre~ (FMC 54 800),cyclol"~ol~ ;ynull..ill, decamethrion, cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)-cycloplo~anecarboxylate, fel,~rop~ll-.in, fenfluthrin, fenvalerate, flu.;yll.,;.-~te7 S flumethrin, fluvalinate, permethrin and re~me1hrin; and l"l,oil.)ides, such as 1-[(6-chloro-3 -pyridinyl)-methyl]-4,5-dihydro-N-nitro- 1 H-imill~7ol-2-anine (imidacloprid).

Possible other active compounds are algicides, molluscicides and active compounds against "sea ~nim~l~" which colonise on, for example, ship's bottom paints.

The active eompound eombinations and agents aeeording to the invention 10 advantageously allow the microbicidal agents hitherto available to be replaced by more effective and more environment~lly comr~tible agents. They display a good stability and advantageously have a broad action ~e~

The following example serves to illustrate the invention without limiting it thereto.
Parts and percentage data denote parts by weight and percentages by weight.

15 ~xample 1 Percent by weight Proportion DDAC 48.44 1.0 Tebuconazole 5.00 0.10 Imidacloprid 0.50 0.010 Iso~lopallol 19.30 Water 26.76 Le A 31 346 - Forei~n countries Test' - ~c and results - -1. Testing storage stability 50-, 75-, 100- and 200-fold dilutions of the test speçimen in water are stored in sealed polyethylene bottles at 2~C and 40~C for 3 months. The dilutions are S then poured into a 1000 ml glass beaker, rated for change in ~,pea~ ce and for the formation of crystals and deposits, and evaluated in accordance with the following criteria:

A: clear solution, no deposits B: slight clouding, but no se-liment~1ion C: severe clouding with se~lim~nt~tion D: obviously destroyed, with cryst~lli7~tion and se~lim~?nt~tion The following stabilities are found:

Dilution rate Storage temperature 2~C 40~C
50-fold A A
75-fold A A
1 00-fold A A
200-fold A B

2. Wood permeability test 50-, 75-, 100- and 200-fold aqueous dilutions of the test specimen are prepared.
Test specimens me~ rin~ 2 cm x 2 cm x 12 cm are cut out from Crvptomeria sapwood; all the surfaces of each of these test specimens, with the exception of ' CA 02238033 1998-05-19 .

I.e A 3 1 346 - Forei~n countries one end face, are sealed with epoxy resin.

10 test specimens each time are weighed and then stored in a 1000 ml glass beaker in such a way that they are unable to float. After storage for 2 hours under vacuum (60 mm Hg) the dilutions are introduced and the test specimens are kept immersed in the dilutions under ~1mosph~ric ~lCS~ for 22 hours. The test specimens are then removed from the dilutions and weighed in order to ~letermine the amount of absorption (kg/m3).

The treated test spe~ men~ are cut open at a ~ t~n-~e of 2 cm and 8 cm from the unsealed end face for analysis of the active compounds DDAC, tebuconazole and imidcloprid after having been stored at 26~C for 1 month under a polyethylene film.

The following results were obtained:

Dilution rate Amount Permeability Arnount introduced of active co~ .u~ d introduced ratio (kg/m3) (o/o) DDAC Tebucon- Imidaclo-azole prid 50-fold 775 100/loO *7.0/5.5 0.7/0.6 0.07/0.06 **78.6% 85.7% 85.7%
75-fold 81û loo/loo 5.0/3.7 0.5/0.4 0.05/0.04 74.0% 80.0% 80.0%
100-fold 707 lûO/lOO 3.0/2.2 0.3/0.2 0.03/0.02 73.3% 66.7% 66.7%
200-fold 778 loo/loo 2.4/1.7 0.2/0.17 0.02/0.015 70.8% 8s.0% 7s.0%

*: 1st No.: 2 cm from the end face; 2nd No.: 8 cm from the end face '' CA 02238033 1998-05-19 Le A 31 346 - Forei~n countries **: Retention ratio 2 cm: 8 cm The result is considered acceptable if the value is above 50% .

3. Testing of fungal rçsiet~nce - -For the tests, 50-, 75-, 100- and 200-fold aqueous dilutions of the test specimen are pl~aLcd. The controls used are 1.0%, 0.7%, 0.5% and 0.3% DDAC in water. In addition, as described in 2.1, test specimens are prepared which are stored at 2~C for 3 months.

Test specimens m~ellnng 2 cm x 2 cm x 10 cm were cut out from cly~ eria sapwood. Rat~hes of 5 of these test specimens are stored in a 1000 ml glass beaker in such a way that they are unable to float. After storage for 2 hours under vacuum (60 mm Hg) the dilutions are introduced and the test specimens are kept imrnersed in the dilutions for 2 hours under atrnospheric ~le3~ul.,. The test specimens are subsequently removed from the dilutions and stored - individually for 21 days under polyethylene filrn.

The treated and u~ ed test specimens are, as described in the standard ENV 807 Parts 1 and 2, stored ~lt~nn~tely in wood-de~lluyillg earth at 26~C
and 90% relative atmc)sphenc humidity for 6 months. After the 6 months, the protection relative to wood-de~L-uyil1g fungi is ~eseesed as fûllows:

A: no attack B: discoloration C: partial destruction D: complete destruction '' CA 02238033 1998-05-19 Le A 31 346 - Foreis~n countries Dilution rate Age of the test dilution prior to impregnation freshly prepared test after 3 months/2~C test specimen specimen S0-fold A A A A A A A A A A
75-fold A A A A A A A A A A
100-fold A A A . A A A A A A A
200-fold A B B A A B A B A A
DDAC 1% C C B C B B C B B C
DDAC 0.7% C C C C C C C C C C
DDAC 0.5% C D D D D D D D D D
DDAC 0.3% D D D D D D D D D D
untreated D D D D D D D D D D

Claims (10)

Claims

1. Active compound combination of at least one azole fungicide, at least one insecticide from the class of the nitromethylenes and at least one quaternary ammonium fungicide.

2. Active compound combination according to Claim 1, containing at least one of the following azole fungicides:

- 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanones (triadimefon) - .beta.-(4-chlorophenoxy)-.alpha.-(1,1-dimethyl-ethyl)-1H-1,2,4-triazole-1-ethanol (triadimenol) - ~ .alpha.-[2-(4-chlorophenyl)-ethyl].alpha.-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol (tebuconazole) - (RS)-2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)-hexan-2-ol (hexaconazole) - 1-(N-propyl-N-(2-(2,4,6-(trichlorophenoxy)-ethyl)-carbamoyl)-imidazole (prochloraz) - 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol - 1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolon-2-yl]-methyl]-1H-1,2,4-triazole(propiconazole) - 1-(2-(2,4-dichlorophenyl)-1,3-dioxolon-2-yl-methyl]-1H-1,2,4-triazole (azaconazole) - (R*,R*)-.alpha.-(4-chlorophenyl)-.alpha.-(1-cyclopropylethyl-1H-1,2,4-triazole-1-ethanol(cyproconazole) and at least one insecticide of the formula especially the compound of the formula and at least one quaternary ammonium fungicide formula (II) in which R1, R2, R3 and R4 are identical or different and in each case representunsubstituted or substituted, straight-chain or branched, saturated or unsaturated alkyl groups having 1 to 20 carbon atoms, alkylaryl and aralkyl groups having 5 to 10 carbon atoms in the aryl part and 1 to 20 carbon atoms in the alkyl part or aryl groups having 5 to 10 carbon atoms, and optionally mono- or polyalkoxylated derivatives hereof;
possible substituents being halogen, C1-C4-alkyl, C1-C4-alkoxy; and wherein 2 or 3 radicals R1 to R4 on the quaternary centre, optionally with further hetero atoms, can form a saturated or unsaturated 5-, 6- or 7-membered (hetercyclic) ring and X represents an anion which promotes water-solubility.

3. Active compound combination according to Claim 1, comprising tebuconazole and/or propiconazole and imidacloprid and C12-C14-alkyl-benzyl-dimethylammonium chloride and/or trimethylcoconut-ammonium chloride and/or didecyldimethylammonium chloride.

4. Microbicidal agents for the preservation of materials, comprising an active compound combination according to Claim 1, solvents or diluents and if appropriate processing auxiliaries and if appropriate other active compounds.

5. Microbicidal agents according to Claim 4, comprising water.

6. Microbicidal agents according to Claim 4, for the preservation of wood and leather.

7. Method of combating microorganisms, characterised in that the active compound combination according to Claim 1 is allowed to act on microbes or their habitat.

8. Use of the active compound combination according to Claim 1 as a microbicide for the preservation of industrial materials.

9. Use according to Claim 8, as a fungicide for the preservation of leather and wood.

10. Use of the active compound combination according to Claim 1 for the preparation of stable, optionally organic-, solvent- and emulsifier-free aqueousmicrobicidal agents.