EP0820370A1

EP0820370A1 - Timber preservative containing a copper compound

Info

Publication number: EP0820370A1
Application number: EP96909162A
Authority: EP
Inventors: Lutz Heuer; Winfried Joentgen; Torsten Groth
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1995-04-12
Filing date: 1996-04-01
Publication date: 1998-01-28
Also published as: SK137297A3; US5874025A; PL322850A1; NO974669L; AU693681B2; JPH11503376A; DE19513903A1; AU5276496A; CZ320097A3; NZ304884A; WO1996032235A1; NO974669D0

Abstract

Novel timber preservative containing at least one copper compound and polyaspartic acid or a derivative thereof, a triazol compound and possibly at least one synergistically supplementing other fungicide and/or insecticide and also possibly an emulsifier and/or some alkanol amine.

Description

Wood preservative containing a copper compound

The application relates to alkanol-free / low-amine wood preservative containing at least polyaspartic acid or its derivatives, a copper compound, a

Triazole compound, which is optionally supplemented with another fungicide and / or insecticide and optionally an emulsifier and / or some alkanolamine.

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP 89 958). The effectiveness of this

In spite of the high copper content, compared to known copper- and chromate-containing salts with a comparable copper content, detergents against wood-destroying Basidiomycetes are not sufficient.

Also known are wood preservatives based on copper compounds and alkanolamines, a triazole compound and an emulsifier or the one

Contain phosphonium compound and have activity against wood-destroying Basidiomycetes (DE 4 112 652 / WO 93/02557 / WO 91/11306).

Also known are synergistic mixtures for protecting wood based on, for example: propiconazole and tebuconazole (EP 393.746, EP 385.076, EP 413.909, EP 548.759, WO 93/02557), optionally using an insecticide as a mixing partner.

The aim and object of the present invention was to find a wood preservative which, firstly, against wood-staining and wood-destroying fungi and against wood-damaging insects, in particular against wood-destroying longhorn beetles (Cerambycidae, Lyctidae, Bostrychidae and

Anobiidae) including termites is highly effective and has a good long-term effect, the effectiveness of the fungicide not being impaired by the insecticide or vice versa. In addition, the wood preservative should have a good penetration into wood and the wood-based materials. It also applies to the loss of alkanolamines caused by evaporation or

Leaching occurs, for ecological and occupational hygiene reasons. This is best achieved if the amount of alkanolamine is significantly reduced (possibly to zero) and another substance takes over its task in whole or in part. Furthermore, the degradation of the organic active substance occurring in contact with the ground in wood and wood-based materials should be prevented. Since this breakdown of the active ingredient does not necessarily take place through wood-destroying and / or wood-staining fungi, but can also take place from other microorganisms associated with them, apart from the synergistically effective mixture of, for example

Tebuconazole and possibly a further fungicide and / or insecticide, the use of a further, biocidal component is necessary in order to achieve a long-term effect of the organic active substances. According to the invention, copper compounds are therefore mixed in, if appropriate in connection with boron derivatives or nitrite-containing salts.

The invention therefore relates to a wood preservative comprising, in addition to a copper compound and polyaspartic acid or a derivative of the like, a triazole compound and, if appropriate, at least one further fungicide and / or insecticide which complements one another synergistically and, if appropriate, an emulsifier and / or some alkanolamine.

Despite the greatly reduced content of alkanolamine, the copper compound is clearly dissolved. Also, no insoluble Cu-polyaspartic acid adducts are observed, as is known in some cases for the Cu ²⁺ + protein biuret reaction.

Despite the content of copper compounds in the wood preservative, the two

When diluted with water, fungicides are clearly distributed, emulsified or dissolved in water. The advantage of the agents according to the invention is that e.g. Triazole compounds which are insoluble in water are present in the new compositions in the form of aqueous emulsions or clear aqueous concentrates. When diluted with water, clear aqueous liquids are formed.

By adding small amounts of organic solvents to the wood preservative, e.g. alcohols (ethanol, isopropanol), glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), glycol ether esters (butyl glycol acetate), dimethylformamide, N-methylpyrrolidone, homogeneous concentrates be preserved. The solvents also act as solubilizers for the fungicides. With the additional use of aryl carboxylic acids, cycloalkyl carboxylic acids or aliphatic C ₅ -C ₂₀ mono- or di carboxylic acids or corresponding amine, Alkali or copper salts, however, the use of solvents can be reduced to a minimum in order to obtain homogeneous concentrates. In any case, the mixture or concentrate contains water as an ingredient.

The copper compounds can be used as water-soluble or water-insoluble compounds, e.g. Copper sulfate, copper acetate, copper hydroxide,

Copper oxide, copper borate, copper fluoride, copper hydroxide carbonate, basic copper carbonate, copper nitrate, copper chloride and copper phosphate.

Another component of the formulation according to the invention is polyaspartic acid, its derivatives or its copolymers with other compounds. For the purposes of the present invention, the corresponding salts of the compounds are also understood as polyaspartic acid, polyaspartic acid derivative and polyaspartic acid copolymer.

The production and use of polyaspartic acid (PAS) and its derivatives has long been the subject of numerous publications and patents.

According to J. Org. Chem., 24, p. 1662-1666, (1959), polysuccinimide, which is referred to there as "anhydropolyaspartic acid", is obtained by thermal polycondensation of maleic acid, malic acid monoammonium salt at temperatures up to 200 ° C. The polymer yields were 75% to 79% at 200 ° C. Malic acid, maleic anhydride, fumaric acid and asparagine are also mentioned as possible starting materials.

The preparation can also be carried out by thermal polycondensation of aspartic acid according to J. Org. Chem. 26, 1084 (1961). The polysuccinimide (PSI), which is also referred to there as "anhydropolyaspartic acid", first appears as an intermediate stage. Hydrolysis can convert PSI into PAS.

US Pat. No. 4,839,461 (= EP-A 0 256 366) describes the preparation of polyaspartic acid from maleic anhydride, water and ammonia. Maleic anhydride is converted into the monoammonium salt in the aqueous medium with the addition of concentrated ammonia solution and then the water is evaporated from the solution. The monoammonium salt is polymerized in bulk. Select During this polymerization, the mass first becomes highly viscous and then solid-porous, which requires handling that is complex in terms of process technology.

From US-A 4 590 260 it is known that amino acids can be polycondensed together with derivatives of malic, maleic and or fumaric acid at 100 to 225 ° C. According to US Pat. No. 4,696,981, such a reaction can be carried out

Use microwaves successfully.

DE-A 2 253 190 describes a process for the preparation of polyamino acid derivatives, especially polyaspartic acid derivatives. Thereafter, in addition to aspartic acid, maleic acid derivatives (monoammonium salt and monoamide) are thermally polymerized to the intermediate stage PSI, which can then be reacted in suitable solvents with amines to give the desired polyamino acid derivatives.

US-A 5 296 578 describes the preparation of PSI from maleic anhydride, water and ammonia. Maleic anhydride is hydrolyzed to maleic acid in water and then with conc. Ammonia solution transferred into the ammonium salt. The water is evaporated from the solution in a stirred reactor and then the monoammonium salt is polymerized in bulk at temperatures above 170 ° C. to give PSI. The mass is converted into solid PSI in several hours over highly viscous phase states and then hydrolyzed to PAS.

US Pat. No. 5,288,783 describes the production of PAS from maleic acid or fumaric acid, water and ammonia. Maleic anhydride is mixed with water in the stirred kettle and converted to maleic acid with cooling. By adding conc. The maleic acid monoammonium salt is produced in ammonia solution. The water contained is then evaporated and the dry monoammonium salt polymerized at temperatures from 190 to 350 ° C. Alternatively, it is proposed to further process the monoammonium salt present in aqueous solution at temperatures of 160 to 200 ° C. by extrusion to give PSI. The PSI produced by one of the two process routes is then hydrolyzed alkaline to PAS.

EP-A 593 187 describes the production of PSI by thermal polymerization of maleic acid at temperatures from 160 to 330 ° C. in a reaction lasts from 2 minutes to 6 hours. Attention is also drawn to the polycondensation in the solvent using condensation aids.

DE-A 4 221 875 describes the production of modified polyaspartic acids by polycondensation and their use as additives for detergents, cleaning agents, water treatment agents and scale inhibitors when evaporating sugars.

The polymers used according to the invention have recurring succinyl units with one of the following structures:

CH ₂ - CO-

, prefers

CH - CO-

CH "- -CO CHr -co- -NH - CH CO - NH

- CH - -co - CH COOH CH, COOH

In addition, further recurring units can be contained by suitable reaction management and choice of the starting materials, for. B.

a) Apple acid units of the formula

b) Maleic acid and fumaric acid units of the formula

c) Iminodisuccinate units of the formula

The chemical structure is preferably analyzed using ¹³ C-NMR, FT-IR and, after total hydrolysis, using HPLC, GC and GC / MS.

For the reaction with a base, the polymerization products can, if appropriate in the presence of water, be converted into a PAS-containing salt. This conversion of PSI-containing to PAS-containing polymers then takes place in a suitable device by hydrolysis. A pH between 5 and 14 is preferably suitable. In a particularly preferred form, a pH of 7 to 12 is chosen, in particular by adding a base. Suitable bases are alkali and alkaline earth metal hydroxides or carbonates such as sodium hydroxide solution, potassium hydroxide solution, soda ash or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines etc. The temperature during the hydrolysis is suitably in a range including up to the boiling point of the PSI suspension and preferably at 20 to 150 ° C. The hydrolysis is optionally carried out under pressure.

However, it is also possible to obtain the free polyaspartic acid by purely aqueous hydrolysis or treatment of the salt with acids or acidic ion exchangers. The term "polyaspartic acid" (= PAS) in the present invention also includes the salts, unless expressly stated otherwise. The finished product is obtained by drying, preferably spray drying.

Depending on the reaction conditions, for example residence time and temperature of the thermal polymerization, the polymer produced shows different chain lengths or molecular weights according to gel permeation chromatography analyzes (Mw = 500 to 10,000, preferably 700 to 5,000, particularly preferably 1,000 to 4,500). In general, the proportion of the beta form is more than 50%, preferably more than 70%.

Another object of the invention is the use of modified polyaspartic acids, which can be obtained by reacting

a) 0.1-99.9 mol% of the aforementioned educts or 0.1-99.9 mol% aspartic acid with b) 99.9-0.1 mol%

of fatty acids, fatty acid amides, polybasic carboxylic acids, their anhydrides and amides, polybasic hydroxycarboxylic acids, their anhydrides and amides, polyhydroxycarboxylic acids, aminocarboxylic acids, sugar carboxylic acids, alcohols, polyols, amines, polyamines, alkoxylated alcohols and amines, amino alcohols , Carbohydrates, ethylenically unsaturated mono- and polycarboxylic acids and their anhydrides and amides, protein hydrolyzates, for example

Maize protein hydrolyzate, soy protein hydrolyzate, aminosulfonic acids and aminophosphonic acids according to the inventive method described above to react.

The starting materials described under a) are used in the polymerization according to the invention to 0.1 to 99.9 mol%, preferably to 60 to 99.9 mol% and particularly preferably to 75 to 99.9 mol%. All fatty acids can be considered as component (b) of the polymers. They can be saturated or ethylenically unsaturated. Examples are formic acid, acetic acid, propionic acid, butyric acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, sorbic acid, myristic acid, undecanoic acid and all naturally occurring fatty acid mixtures, for example C ₁₂ / C ₁₄ - or C ₁₆ / C _lg -Fatty acid mixtures. Acrylic acid and methacrylic acid can also be used as unsaturated fatty acids.

Furthermore, these acids can also be used in the form of their amides. Examples of polybasic carboxylic acids are oxalic acid, succinic acid, glutaric acid, adipic acid, malonic acid, suberic acid, aconitic acid, itaconic acid, sulfosuccinic acid, alkenylsuccinic acids (C, -C ₂₆ ), 1,2,3, propanetricarboxylic acid, butane tetracarboxylic acid, furanedicarboxylic acid and pyridinedicarboxylic acid be used. The anhydrides of polybasic carboxylic acids such. B. succinic anhydride, itaconic anhydride, aconitic anhydride and phthalic anhydride can be used. Coming in as component (b) are also polybasic

Hydroxycarboxylic acids and polyhydroxycarboxylic acids into consideration. In addition to at least one hydroxy group, polybasic hydroxycarboxylic acids carry at least two or more carboxyl groups. Malic acid, tartaric acid, grape acid, citric acid and isocitric acid are mentioned as examples here.

In addition to a carboxylic acid group, monobasic polyhydroxycarboxylic acids carry two or more hydroxyl groups, for example glyceric acid, dimethylolpropionic acid, dimethylolbutyric acid and gluconic acid. In addition, monohydric alcohols with, for example, 1 to 22 carbon atoms, such as. As methanol, ethanol, n-propanol, i-propanol, butanol, pentanol, hexanol, octanol, lauryl alcohol, stearyl alcohol, etc. are suitable. The alcohols can also optionally have a double bond, such as allyl alcohol or oleyl alcohol. Furthermore, these alcohols can be alkoxylated, for example with ethylene oxide or propylene oxide. The adducts of 3 to 50 moles of ethylene oxide with fatty alcohols or oxo alcohols are of particular technical interest. Furthermore, as component (b) polyols can be used either saturated or unsaturated, such as. B. ethylene glycol, propylene glycol, butanediol, butenediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, neopentylglycol and alkoxylated polyols such as polyethylene glycols, polypropylene glycols, ethoxylated trimethylolpropane, glycerol or pentaerythritol with molecular weights up to 6000 can be used. Also suitable as comonomer (b) are amines such as C 1 -C ₂₂ -alkylamines, e.g. B. methylamine, ethyl amine, propylamine, butylamine, cyclohexylamine, octylamine, isooctylamine (ethylhexylamine), stearylamine, allylamine, oleylamine, ethylenediamine, diethylenetriamine, hexamethylenediamine, piperazine, diaminobutane, dimethylamine, diethylamine, hydroxylamine, hydrazine, as well as amine amine, ethanolamine, polyamine, amine amine, polyamine, amine amine, as well as amine, amine amine, and amine amine, such as amine, amine amine, and amine amine, as well as amine, amine amine, and amine amine, as well as amine, amine amine, and amine amine, as well as amine, amine, and amine amine, as Polyethylene amine with molecular weights up to 6000. The

Amines can also be alkoxylated, e.g. the adducts of 3 to 30 moles of ethylene oxide with fatty amines such as oleylamine, palmitylamine or stearylamine. Aminosugars such as aminosorbitol or chitosamine are also suitable. In addition, component (b) are carbohydrates such as glucose, sucrose, maltose, dextrins, starch or sugar carboxylic acids, for example mucic acid, gluconic acid, glucuronic acid, glucaric acid. In addition, amino acids, protein genes such as glycine, alanine, glutamic acid and lysine or non-proteinogens such as 4-aminobutyric acid, diamino-succinic acid, 11-aminoundecanoic acid and 6-amino-caproic acid can be used as component (b). The compounds of component (b) are used in amounts of 0.1 to 99.9 mol%, preferably 0.1 to

40 mol%, particularly preferably 0.1 to 25 mol%, are used for the polymerization. A single compound of component (b) or mixtures of two or more compounds of (b) can be used.

If monofunctional compounds such as alcohols, amines, fatty acids or fatty acid amides are used as component (b), they are incorporated at the chain end. They act as chain terminators and lower the molecular weight. Multi-functional compounds of component (b) can be incorporated in the finished polymer both at the chain end and also randomly distributed over the polymer chain.

The crude polymers can be freed from monomeric fractions by customary workup methods, for example by extraction with water and 1N hydrochloric acid or by membrane filtration. The copolymers are analyzed by ¹³ C and ⁵ N NMR spectroscopy, FT-IR spectroscopy and after total hydrolysis with HPLC, GC and GC-MS. In the polymerization according to the invention, the polymer is obtained primarily in the form of the mostly water-insoluble modified polysuccinimides.

The modified polyaspartic acids are prepared from the polysuccinimides, preferably by aqueous hydrolysis at 20 ° C. to 50 ° C. and pH 7 to 12, if appropriate under pressure. This reaction can also be found in Carry out temperatures outside the specified temperature range and at other pH values. Suitable bases are alkali and alkaline earth metal hydroxides or carbonates such as, for example, sodium hydroxide solution, potassium hydroxide solution, sodium carbonate or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines, etc. Partially or completely neutralized copolymers obtained from 0.1 to Contain 99.9 mol% aspartic acid and 99.9 to 0.1 mol% of at least one compound (b) in copolymerized form.

An alkanolamine is especially monoethanolamine; the use of other alkanolamines e.g. Isopropanolamine 1,1-, 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine, N-methylaminoethanol, N-ethylaminoethanol, ethanolhydrazine, N-butylaminoethanol, N-phenylaminoethanol and (2-aminoethoxy) ethanol are possible .

The amount of added polyaspartic acid / its derivatives and, if appropriate, some alkanolamines is advantageously such that a pH of 4 or more, preferably 8.5 to 10.5, is established in the dilute aqueous impregnation solution. The amount of polyaspartic acid / and derivatives and the amines should be sufficient to complex the copper.

Synergistic mixtures of triazole compounds such as e.g. Tebuconazole, preferably with one or more fungicides from the series:

Azaconazole, bromuconazole, cyproconazole, dichlobutrazole, diniconazole, hexaconazole, metconazole, penconazole, epoxyconazole, methyl- (E) -methoximino [α- (o-tolyloxy) -o-tolyl)] acetate, methyl- (E) -2 - {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy] phenyl} -3-methoxyacrylate, methfuroxam, carboxin, fenpiclonil, 4 (2,2-difluoro-1,3-benzodioxol-4- yl) - 1H-pyrrole-3-carbonitrile, butenafine, 3-iodo-2-propynyl-n-butylcarbamate (IPBC) and / or polymeric quaternary ammonium borates

(known from EP 355 316 and EP 556 454).

The following fungicides or insecticides are also preferably used as synergistic fungicidal or insecticidal mixing partners. Triazole e:

Amitrole, Azocyclotin, Bitertanol, Fenbuconazole, Fenchlorazole, Fenethanil, Fluquinconazole, Flusilazole, Flutriafol, Imibenconazole, Isozofos, Myclobutanil, Met- conazole, Epoxyconazole, Paclobutrazol, (±) -cisphenyl-l- (lH-1,2,4-triazole-l -yl) cycloheptanol, tetraconazole, triadimphone, triadimenol,

Triapenthenol, Triflumizole, Triticonazole, Uniconazole as well as their metal salts and acid adducts.

Imidazole:

Imazalil, pefurazoate, prochloraz, 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-4'-trifluoromethyl-1, 3-thiazole-5-carboxanilides and their metal salts and acid adducts.

Methyl (E) -2- [2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl] 3-methoxyacrylates, methyl 1 (E) -2- [2- [6- (2-thioam dophenoxy) pyrimi din-4-y 1 oxy] pheny 1] -3-methoxy acrylate, methyl (E) -2- [2- [6- (2-fluorophenoxy) pyrimidin-4-yloxy] phenyI] -3 -methoxyacrylate, methyl (E) -2- [2- [6- (2,6-difluorophenoxy) pyrimidin-4-yloxy] phenyl] -3-methoxy-acrylate, methyl (E) -2- [2- [3- (pyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (5-methylpyrimidin-2-yloxy) phenoxy] phenyl] -3-methoxyacry - late, methyl (E) -2- [2- [3- (phenylsulfonyloxy) phenoxy] phenyl] -3-methoxyacrylates, methyl (E) -2- [2- [3- (4-nitrophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) - 2 - [2-phenoxy pheny 1] -3-methoxy acrylate, methyl (E) -2- [2- (3, 5 - dimethylbenzoyl) pyrrole -1-yI] -3-methoxy acrylates, methyl (E) -2- [2- (3-methoxyphenoxy) phenyl] -. 3-methoxyacrylates, methyl (E) -2- [2- (2-phenylethen-1 -yl) - phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3,5-dichlorophenoxy) pyridin-3-yl] -3- methoxyacrylate, methyl (E) -2- (2- ( 3- ( 1, 1, 2,2-tetrafluoroethoxy) phenoxy) phenyl) -3- methoxyacrylate, methyl (E) -2- (2- [3- (alpha-hydroxybenzyl) phenoxy] phenyl) -3- methoxyacrylate, methyl (E) -2- (2- (4-phenoxypyridin-2-yloxy) phenyl) -3- methoxyacrylate, methyl (E) -2- [2- (3-n-propyloxyphenoxy) phenyl] 3-methoxyacrylate, methyl (E ) -2- [2- (3-isopropyloxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (2-fluorophenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl ( E) -2- [2- (3-ethoxyphenoxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (4-tert-butylpyridin-2-yloxy) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [3- (3-cyano-phenoxy) phenoxy] phenyl] -3-methoxyacrylate, methyl (E) -2- [2- (3-methylpyridine-2- yloxymethyl) phenyl] -3-methoxyacrylate, methyl (E) -2- [2- [6- (2-methylphenoxy) pyriminin-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-methoxyacrylate, methyl (E) -2- [2- [6- (2-chloropyridin-3-yloxy) pyrimidin-4-yloxy] phenyl] -3-methoxyacrylates, (E), (E) methyl-2- [2- (5th , 6-dimethylpyrazin-2-ylmethyloximinomethyl) phenyl] -3-methoxyacrylate, (E) -methyl- 2- {2- [6- (6-methylpyridin-2-yloxy) pyrimidin-4-yloxy] phenyl} -3- methoxyacrylates, (E}, (E) methy 1-2- (2- (3-methoxyphenyl) methyloximinomethyl] phenyl} -3-methoxyacrylates, (E) methyl-2- {2- (6- (2-azidophenoxy ) -pyrimidin-4-yloxy] phenyl} 3-m ethoxyacrylate, (E), (E) methy 1 -2- {2- [6-phenylpyri di n-4-yl) methyloximinomethyl] 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-methoxy acrylates, ( E), (E) methyl-2- {2 - [(3-nitrophenyl) 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, butenafine, 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, thiophonate methyl, thiabendazole or their salts;

Morpholine derivatives such as Tridemoφh, Fenpropimorph, Falimorph, Dimethomorph, Dodemorph; Aldimorph, fenpropidine and their aryl sulfonic acid salts, such as, for example, 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, paraformadehyde, nitropyrin, oxolinic acid, tecloftalam;

Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) - tributyltin or K salts, bis-N- (cyclohexyldiazeniumdioxy) copper.

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octylisothiazolin-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, didecyldimethaylammonium chloride;

Iodine derivatives such as diiodomethyl p-tolyl sulfone, 3-iodo-2-propynyl alcohol, 4-chlorophenyl-3-iodopropargyl formal, 3-bromo-2,3-diiodo-2-propenylethyl carbamate, 2,3,3-tri- iodallyl 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-iodo-2-propynylphenyl carbamate;

Phenol derivatives such as tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol, 2-benzyl-4-chlθφhenol and their alkali - and

Alkaline earth metal salts.

Microbicides with activated halogen group such as chloroacetamide, bronopol, bronidox, tectamer such as 2-bromo-2-nitro-l, 3-propanediol, 2-bromo-4'-hydroxy-aceto- phenone, 2,2-dibromo-3-nitrile-propionamide, 1,2-dibromo-2,4-dicyanobutane, ß-bromo-ß-nitrostyrene;

Pyridines such as l-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulfonylpyridine, pyrimethanol, mepanipyrim, dipyrithione;

Metal soaps such as tin, copper, zinc naphtenate, octoate, 2-ethylhexanoate, oleate,

-phosphate, -benzoate;

Metal salts such as sodium dichromate, potassium dichromate, potassium chromate, 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-tetrahydro-l, 3, 5-thiadiazin-2-thione, N- (2-p-chlorobenzoylethyl) hexaminium chloride, potassium N-hydroxymethyl-N'-methyldithiocarbamate, 2-oxo-2- (4-hydroxyphenyl) acethydroximic acid chloride,

Phenyl- (2-chloro-cyanovinyl) sulfone, phenyl- (1,2-dichloro-2-cyanovinyl) sulfone;

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

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, α-l (4-chlorophenyl) -4-

(O-ethyl, S-propyl) phosphoryloxy-pyrazole, Chloφyrifos, 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) silyl methyl 3-phenoxybenzyl ether such as dimethyl (4-ethoxyphenyl) silylmethyl 3-phenoxybenzyl ether or

(Dimethylphenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether such as e.g. Dimethyl

(9-ethoxy-phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ether or [(phenyl) -3- (3-phenoxyphenyl) propyl] (dimethyl) silanes such as e.g. (4-ethoxyphenyl) - [3- (4-fluoro-3-phenoxyphenyl-propyl-dimethyl-silane, silafluofen;

Pyrethroids such as allethrin, alphamethrin, bioresmethrin. Byfenthrin, cycloprothrin, cyfluthrin, 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 l - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-lH-imidazol-2-amine (idacloprid), N - [(6-chloro 3-pyridyl) methyl-] N -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-phosphorus - cyclam, thiofanox, thiometone, tralomethrin, triflumuron, trimethacarb, vamidothion, verticillium lacanii, XMC, xylylcarb, benfuracarb, bensultap,

Bifenthrin, bioallethrin, MERbioallethrin (S) -cyclopentenyl isomer, bromophos, Bromophos-ethyl, Buprofezin, Cadusafos, Calcium Polysulfide, Carbophenothion, Cartap, Chinomethionate, Chlordane, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chloropicrin, Chloφyrifos, Cyanophos, Beta-Cyfluthrin, Alpha- cypermethrin, Demazomotomhrin, Cyazhenotom, - methylsulphone, diafenthiuron, dialifos, dicrotophos, diflubenzuron, dinoseb,

Deoxabenzofos, Diaxacarb, disulfoton, DNOC, empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion, etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil, flucycloxuron, flufenprox, flufenoxuron, fonofos, Formetanate, formothion, Fosmethilan, furathiocarb, heptachlor, hexaflumuron, Hydramethylnon, Hydrogen Cyanide, Hydroprene, IPSP, Isazofos, Isofenphos, Isoprothiolane, Isoxathion, Iodfenphos, Kadethrin, Lindane, Malathion, Mecarbam, Mephosfolan, Mercurous, Chloride, Metam, Metarthitik, anisopliae, Methacrifoc, Methathophi, Metharbophi, Methamidophoxy , Methyl isothiocyanate, Metholcarb, Mevinphos, Monocrotophos, Naled, Neodiprion sertifer NPV, Nicotine, Omethoate, Oxydemeton-methyl, Pentachlorophenol,

Petroleum oils, phenothrin, phenthoates, phorates;

Particularly preferred mixtures contain as insecticides:

Chloφyrifos, phoxim, silafluofen, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, hexaflunuron, lindane.

The use of tebuconazole as the sole fungicide or synergistic mixture of is particularly preferred

- Tebuconazole and cyproconazole and optionally bromoconazole and / or hexaconazole and or propiconazole and / or Tridemoφh

- Tebuconazole and metconazole and optionally cyproconazole and / or hexaconazole and / or tridemorph

- Tebuconazole and Hexaconazole and optionally Cyproconazole and / or Metconazole and / or Bromoconazole and / or Tridemoφh

- Tebuconazole and l- (2-chlorophenyl) -2- (l-chloro-cycloprop-l-yl) -3- (l, 2,4-triazol-1-yl) -propan-2-ol and optionally cyproconazole and / or Metconazole and / or Bromoconazole and / or Hexaconazole and / or Tridemoφh Tebuconazole and Tridemoφh and optionally cyproconazole and / or propiconazole and / or bromoconazole and / or hexaconazole and / or penconazole,

- Tebuconazole and propiconazole and optionally cyproconazole and / or bromoconazole and / or hexaconazole and / or metconazole and / or Tride¬ moφh and / or penconazole and / or l- (2-chlorophenyl) -2- (l-chlorocycloprop-l-yl ) -3- (1, 2,4-triazol-1-yl) propan-2-ol

- Cyproconazole and Bromoconazole and / or Metconazole and / or Hexaconazole and / or Tridemoφh,

Hexaconazole and bromoconazole and / or metconazole and / or penconazole and or tridemoφh,

- Penconazole and cyproconazole and / or metconazole and / or bromoconazole and / or tridemoφh.

The synergistic effect of the mixtures is very preferably in a ratio of 99: 1 to 1:99, preferably 3: 1 to 1: 3

1: 1 observed.

The ratio of copper ions to the sum of the fungicide mixture should be at least 1: 2.5 to 1000: 1; mixtures with 5: 1 to 500: 1 are preferred, very particularly preferably 10: 1 to 100: 1.

Additive boron salts or boric acid as well as nitrite (e.g. sodium nitrite) are in

With respect to the copper ions in a ratio of 1:50 to 50: 1, preferably to be added. The exact amount is to be based on the particular fungicide mixture and, like the amount of any emulsifier to be added, depends on the water solubility of the finished mixture obtained.

An emulsifier is, for example, an anionic, cationic or nonionic

Emulsifier or a mixture thereof. Nonionic emulsifiers are, for example, addition products of ethylene oxide (EO) or propylene oxide or mixtures thereof with organic hydroxy compounds, for example al ylphenols, fatty acids, fatty alcohols and mixtures thereof. As cationic emulsifiers For example, quaternary ammonium compounds and or salts of fatty amines (for example dimethyl- (C ₁₂ -C ₁₄ ) alkylamine) can be used.

The polymeric quaternary ammonium borates are substances which are obtained by simultaneous reaction of amines of the general formulas I or II

R ² R ⁴ R ⁶

_{D 1} / \ /

R - N 0), N - A - N (ll),

\ ₃ / \ 7

R ³ R ⁵ R

with 2 to 20, preferably 3 to 10, moles of ethylene or propylene oxide and 0.6 to 1.5, preferably 1 mole of boric acid, boric acid ester or salts of boric acid, in each case per mole of nitrogen equivalent, where R ^{1 is} C ₈ -C ₂₂ -alkyl or C ₈ -C ₂₂ alkenyl or, if R ² and R ^{3 represent} groups of the formula - (C ₂ H ₄ O) _x H or - ^ HgO ^ H, R ^{1 can} also mean C _r C ₄ alkyl, R ^{2 is} hydrogen, C ₁ -C ₂₂ alkyl or a group of the formulas - (C ₂ H ₄ O) _x H, - (^ H ^ H or CH ₂ CH ₂ CH ₂ NH ₂ , R ⁴ and R ^{6 is} C _] -C ₄ alkyl or a group of the formulas - (C ₂ H ₄ O) _x H or - (C ₃ H ₆ O) _x H, R ⁵ and R ^{7 are} a group of the formula - (C ₂ H ₄ O) _x H or - (C ₃ H ₆ O) _x H, A is a group of the formulas - (CH ₂ ) _n -, - (CH ₂ CH ₂ OCH ₂ OH) _n - or - (CH ₂ CH ₂ NHCH ₂ CH ₂ ) _n -x numbers from 1 to 55 and n an integer from 1 to

20 mean.

The following are preferred as amines of the above formulas:

1. Amides of the formula I, where R ^{1 is} C ₈ -C ₂₂ alkyl, R ² C ₈ -C ₂₂ alkyl or C _r C ₄ alkyl and R ^{3 is} hydrogen or a group of the formulas - (C ₂ H ₄ O ) _x H or - (C ₃ H ₆ O) _x H mean.

2. Amines of the formula I, where R ^{1 is} C ₈ -C ₂₂ alkyl and R ² and R ^{3 are} hydrogen.

3. Amines of the formula I, where R ¹ C _r C ₄ alkyl or C ₈ -C ₂₂ alkyl and R ² and R ³ groups of the formulas - (C ₂ H ₄ O) _x H or - (C ₃ H ₆ O) _x H, the sum of the ethylene oxide groups in both radicals R ² and R ^{3 being} 2 to 20. 4. Amines of the formula I, where R ^{1 is} C ₈ -C ₂₂ alkyl, R ^{2 is} hydrogen or a group of the formula -CH ₂ CH ₂ CH ₂ NH ₂ and R ^{3 is} a group of the formula -CH ₂ CH ₂ CH ₂ NH ₂ mean.

5. Amines of the formula II, where A, R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above and where the sum of all ethylene oxide groups 4 to

30 is.

In the case of the alkylene oxide groups of the formulas - (C ₂ H ₄ O) _x H and - (C ₃ H ₆ O) _χ H, the group of the formula - (C ₂ H ₄ O) _x H is preferred. Instead of the pure polyoxethylene and polyoxpropylene groups, there may also be residues which are composed of both ethylene oxide and propylene oxide units.

The amines are reacted with the boric acid and the alkylene oxide in such a way that the respective amine and the boric acid are introduced into an autoclave and the alkylene oxide is metered in. The reaction temperature is generally 60 to 130 ° C, preferably 60 to 125 ° C, in particular 60 to 100 ° C. The reaction pressure is 50 to 600 kPa. The alkylene oxide is metered in under these reaction conditions over a period of 1 to 5 hours. For the after-reaction, the mixture is kept at the indicated pressure for 3 to 12 hours at a temperature of 70 to 120 ° C, preferably 70 to 100 ° C.

Instead of boric acid, its esters, e.g. Trimethyl boric acid esters or their salts, for example Na borate, can be used. Water and polyglycols are formed as by-products in the reaction.

The polymeric quaternary ammonium compounds obtained essentially contain groups of the formula as a structural feature

or groups of the formula © N - A © - NI - (CH ₂ CH ₂ 0) _x BI - (OCH ₂ CH ₂ ) _y O - BI - (OCH ₂ CH ₂ ) _z

R ⁵

if the reaction was done with ethylene oxide. They are to be regarded as polymer betaines.

Compounds of the above type and their preparation are described in EP-556 454 and EP-355 316.

A quaternary ammonium compound is, for example, a compound corresponding to the general formula R * R ² R ³ R ⁴ N + Z-, where

R ^{1 is} an alkyl radical with 8 to 20 carbon atoms, in particular an alkyl radical with 12 to 20 carbon atoms or a benzyl radical which is optionally substituted by C 1 -C ₂₀ -alkyl or halogen,

R ² C _r to C ₆ alkyl, C ₃ to C ₉ alkoxyalkyl, polymeric ethylene oxide (EO) or propylene oxide (PO) with EO or PO n = 2 to 50,

R ³ C _r to C ₆ alkyl, C ₃ - to C ₄ alkoxy, polymer ethylene oxide (EO) or propylene oxide (PO) with EO or PA n = 2 to 50,

R ⁴ C _r to C ₂₀ alkyl

means or each two of the radicals R ¹ to R ⁴ together with the nitrogen atom form a heterocyclic radical which contains 4 to 5 carbon atoms and one, two or three double bonds, the carbon atoms optionally by C _r to C ₄ alkyl or halogen are substituted and Z is an acid residue, e.g. B. halide means.

Aliphatic carboxylic acids can be added to improve the homogeneity of the concentrates. Examples of such acids are propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as 2-ethylhexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as sebacic acid, cycloalkylcarboxylic acids such as cyclohexanoic acid, arylcarboxylic acids such as benzoic acid, 3- or 4-hydroxybenzoic acid or alkoxybenzoic acid, tartaric acid or glycine or the salts of the acids such as sodium, potassium salts.

When using the abovementioned acids, it is sometimes advantageous to add complex-forming, polymeric nitrogen compounds such as e.g. Polyethyleneimines improve the penetration of wood preservatives in large-scale processes.

Polyethyleneimines (PEI, polymine) are known and are formed by polymerizing 1,2-ethyleneimine. In them the nitrogen is primary (end group), secondary and tertiary (branching). Polyethyleneimines with n greater than 10 are suitable; very good results are achieved when using PEI with a

Degree of polymerization n between 50 and 1,000. Polylysines (Sigma) can also be used.

The wood preservatives may optionally contain other compounds, e.g. Compounds with a fungicidal anion such as a boron compound (e.g. alkali borate, amine borate, boric acid, boric acid ester), fluorides (e.g. potassium fluoride and / or salts of fluoroboric acid and / or fluorophosphoric acid and / or di-fluorophosphoric acid).

The range of action of the wood preservatives according to the invention can optionally be improved by the addition of further active ingredients. Suitable connections are e.g. N-organodiazenium dioxy compounds, organotin compounds, especially tributyl (TBT) tin compounds, isothiazoline compounds of the following formula

R ¹ is hydrogen, an alkyl, alkenyl, alkynyl radical with 1 to 18 carbon atoms, cycloalkyl radical with a C ₃ to C ₆ ring and with up to 12 carbon atoms, an aralkyl or aryl radical with up to 19 Carbon atoms, R ² , R ³ independently of one another hydrogen, halogen or C, - to C ₄ -alkyl radical or R and R part of an aromatic radical or

R ² - R ⁶ form -CH ₂ -CH ₂ -CH ₂ -.

It is also possible to add other fungicides or insecticides, e.g. in emulsified form, like

N-tridecyl-2,6-dimethylmoφholin (Tridemoφh) and / or

4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmoφholin (Fenpropi- moφh) and / or Aldimoφh, chlorinated phenols

Tetrachloroisophthalic acid dinitrile,

N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, N-dimethyl-N'-phenyl- (N-fluoromethylthio) sulfamide, N, N-dimethyl-N'-toluyl- (N fluoromethylthio) sulfamide, benzimidazole-2-carbamic acid methyl ester,

2-thiocyanomethyl-thiobenzothiazole, 2-Iodbenzoesäureanilid, l- (l ', ^2, ^{4'-triazolyl-l,)} - (l- ^(4, -chloφhenoxy) -3,3-dimethyl-butan-2-on, 1 - (1 ^■ , 2 ', 4'-triazolyl-1') - (1 - (4'-chloro-phenoxy) -3, 3-dimethylbutan-2-ol, hexachlorocyclohexane,

0,0-diethyl-dithio-phosphoryl-methyl-6-chlorobenzoxazolone, 2- (1,3-thiazol-4-yl) -benzimidazole, N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide, N- (l , l, 2,2-tetrachloroethylthio) -3,6,7,8-tetrahydrophthalimide, N-trichloromethylthiophthalimide.

3-iodo-2-propylbutyl carbamate,

O, O-dimethyl-S- (2-methylamino-2-oxoethyl) dithiophosphate, O, O-dimethyl-O- (3,5,6-trichloro-2-pyridyl) thiophosphate, O, O-dimethyl- S- (N-phthalimido) methyldithiophosphate, O, O-diethyl-O- (α-cyanobenzylidene-amino) thiophosphate,

6, 7, 8,9, 10-hexachlor, l, 5.5 a, 6.9.9a-hexahydro-6.9-methanol-2,3, 4-benzoedioxothiepien-3-oxide,

(4-ethoxyphenyl) - (dimethyl) - (3- (4-fluoro-3-phenoxyphenyl) propyl silane,

2-sec-butyl-phenyl-N-methylcarbamate, 2-1-propoxyphenyl-N-methyl-carbamate, N-methyl-1-naphthyl-carbamate, norbornene-dimethanohexa-chlorocyclosulfite, l- (4-chloro-phenyl) -3- (2,6-di-fluorobenzoyl) urea.

Acypetacs, 2-aminobutanes, ampropylfos, anilazines, benalaxyl, bupirimate,

Quinomethionate, Chloroneb, Chlozolinate, Cymoxanil, Dazomet, Diclomezine, Dichloram, Diethofencarb, Dimethirimol, Diocab, Dithianon, Dodine, Drazoxolon, Edifenphos, Ethirimol, Etridiazole, Fenarimol, Fenitropan, Flomidulamone, Hydroxidomamidone, Fentinamide, Fentin acetate, Flutriafol, Fosetyl, Fthalide, Furalaxyl, Guazatine, Hymexazol, Iprobefos, Iprodione, Isoprothiolane,

Metalaxyl, Methasulfocarb, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadiyl, Perflurazoate, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Procymidone, Propamocarb, Propineb, Pyrazophos, Pyrifenox, Pyroquilon, Quinticyeneazole, Tolo -methyl, triazoxides, trichlamides, tricyclazoles, triforins, vinclozolin.

Surprisingly, these combinations of active substances have a particularly high, co-microbicidal, in particular fungicidal activity, combined with a broad spectrum of activity against microorganisms and insects relevant in wood protection; they are particularly effective against mold, wood-staining and wood-destroying fungi and insects. The following groups of microorganisms may be mentioned by way of example, but without limitation:

A: Wood-staining fungi:

AI: Ascomycetes

Ceratocystis such as Ceratocystis minor

A2: Deuteromycetes:

Aspergillus like Aspergillus niger

Aureobasidium such as Aureobasidium pullulans

Dactylium such as Dactylium fusarioides

Penicillium such as Penicillium brevicaule or Penicillium variabile

Sclerophoma such as Sclerophoma pithyophila

Acopularia such as Scopularia phycomyces Trichoderma such as Trichoderma viride or Trichoderma lignorum

A3: Zygomycetes:

Mucor like Mucor spinorus

Wood-destroying mushrooms:

B 1: Ascomycetes:

Chaetomium such as Chaetomium globosum or Chaetomium alba-arenulum Humicola such as Humicola grisea Petriella such as Petriella setifera

Trichurus like Trichurus spiralis

B2: Basidiomycetes:

Coniophora like Coniophora puteana

Coriolus like Coriolus versicolor Donkioporia like Donkioporia expansa

Glenospora such as Glenospora graphii

Gloeophyllum such as Gloeophyllum abietinum or

Gloeophyllum adoratum or Gloeophyllum protactum or

Gloeophyllum sepiarium or Gloeophyllum trabeum Lentinus such as Lentinus cyathiformes or

Lentinus edodes like Lentinus lepideus or

Lentinus grinus or Lentinus squarrolosus

Paxillus such as Paxillus panuoides

Pleurotus such as Pleurotus ostreatus Poria such as Poria monticola or Poria placenta or

Poria vaillantii or Poria vaporaria

Seφula like Seφula himantoides or

Seφula lacrymans

Stereum like Stereum hirsutum Tyromyces like Tyromyces palustris

B3: Deuteromycetes

Altemaria such as Alternaria tenius Cladosporium such as Cladosporium herbarum Alternaria tenuis

C. Wood-destroying insects like

Cl: Beetle Hylotrupes bajulus. Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticomis, Dendrobium pertinex, Emobius mollis, Priobium caφini, Lyctus brunneus, Lyctus africanus, Lyctus Planicollodendus, specus, specus, specus Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus

C2: Skin wing

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur

C3: termites Kaloter es flavicollis, Cryptotermers brevis, Heterotermes indicola,

Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.

The amount of the agents or concentrates used depends on the type and occurrence of the insects, microorganisms, the number of bacteria and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.001 to 20% by weight, preferably 0.05 to 10% by weight, of the active compound mixture, based on the material to be protected.

The insecticides are generally in an application concentration of

0.00001% to 10%, preferably 0.00001% to 5%, particularly preferably 0.001% to 1%.

The formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with a solvent or diluent, emulsifier, dispersant and / or binder or fixative, water re- pellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids.

In addition to water, an organic-chemical solvent or solvent mixture and / or an oily or oil-like low-volatile organic-chemical solvent or may be used as the solvent and / or diluent

Solvent mixture and / or a polar organic chemical solvent or solvent mixture.

The organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.

Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° are advantageous C, Teφentinöl and the like. For use.

In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or spindle oil and / or monochloronaphthalene, preferably α- Monochlomaphthalene used.

The organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture is also a Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture. According to a preferred embodiment, aliphatic organochemical solvents containing hydroxyl and / or ester and / or ether groups, such as, for example, glycol ethers, esters or the like, are used.

In the context of the present invention, the known water-thinnable synthetic resins and / or soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders, exist as organic chemical binders from or containing an acrylic resin, a vinyl resin, for example Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, preferably with a medium oil length, phenolic resin,

Hydrocarbon resin such as inden-coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin are used.

The synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.

According to the invention, at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder. Alkyd resins having an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.

All or part of the binder mentioned can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight glycol ether, glycerol ester and p-toluenesulfonic acid ester.

Fixatives are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

In addition to these aids, those described in EP-383 746,

Pages 5-6 described aids used as a component for wood preservatives.

By wood, which can be protected by the agent according to the invention or mixtures containing it, is to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood , Chipboard, carpentry or wood products that are used in general in house construction or joinery. Particularly effective wood protection is achieved through large-scale impregnation processes, e.g. Vacuum, double vacuum or pressure processes.

The water-thinnable wood preservatives generally contain - in concentrated form - the triazole / fungicide or insecticide mixture in amounts of 0.01 to 95% by weight, in particular 0.01 to 60% by weight.

The water-thinnable wood preservatives contain - in concentrated form - the copper calculated as metal in general, e.g. in an amount of 1.0 to

15.0% (weight percent).

Suitable concentrates are e.g. out

0.50 to 45% copper compounds

5.00 to 50% polyaspartic acid or its derivatives 0 0,, 2255 biss 1 155%% synergistic triazole / fungicide or insecticide mixture

0.5 to 30% of an emulsifier and / or a phosphonium compound and / or tridemorph or Aldimoφh

0 to 40% compound with a fungicidal inorganic or organic anion

0 to 40% organic solvents 0 to 40% of an aliphatic mono- or dicarboxylic acid and / or

Cycloalkylcarboxylic acid and or cycloarylcarboxylic acid and / or boric acid or a borate

0 to 15% of a complex-forming, polymeric nitrogen compound 0 to 5% alkanolamine

where the sum is 100% by weight, as well as minor amounts of other components, such as Ammonia, corrosion inhibitors, complexing acids (e.g. nitrilotriacetic acid, ethylenediaminetetraacetic acid when using water with higher degrees of hardness) and, if necessary, water, the proportion of which, however, can generally be kept low and which essentially serves for handling.

However, in addition to the wood preservatives (concentrates), the invention also extends equally to the impregnation solutions which can be prepared by diluting the concentrates with water in accordance with a lower individual concentration. The application concentration is e.g. 0.01 to 1.50% by weight of metal, e.g. Copper, in the aqueous impregnation solution, depending on the type of impregnation and the degree of hazard of the wood to be impregnated.

Highly concentrated pastes are formed by dissolving the copper salts, if necessary with the supply of heat, in polyaspartic acid / their derivatives, if appropriate with addition of acid, water, alkanolamine or solvent, and then adding the emulsifier, the triazole compounds and the synergistic mixing partner. liquid concentrates or two-phase mixtures that can be used to impregnate wood after dilution with water. They produce a clear liquid even at high concentrations in water.

The use of impregnation solution for protecting wood can be carried out by manual processes such as spraying, brushing, dipping, troughs or by large-scale processes such as boiler pressure processes, alternating pressure processes, double vacuum processes. "Wood" means both solid wood and wood-based materials such as chipboard and plywood; if necessary, the wood preservative can also be mixed in with the lei.

The copper fixation of the wood preservatives according to the invention is high; when used for industrial processes, it is more than 90%. The concentrates or solutions can be colored using water-soluble or water-emulsifiable dyes and / or pigment preparations.

It is possible to add wax, paraffin and / or acrylate dispersions to achieve a water-repellent effect or to improve the fixation.

If necessary, the concentrates can also be incorporated into binder-containing water-thinnable systems (primers, glazes).

The means according to the invention advantageously make it possible to replace the previously available means with more effective ones. They show good stability and advantageously have a broad spectrum of activity.

Claims

claims

1. Wood preservative, characterized by a content

at least one copper compound and polyaspartic acid or a derivative of the like,

- on a triazole compound and

if necessary, on at least one further fungicide and / or insecticide which complement one another synergistically and

optionally on an emulsifier and / or some alkanolamine.

2. Use of mixtures that

- At least one copper compound and polyaspartic acid or

Derivative like that

a triazole compound and

if appropriate, at least one further fungicide and / or insecticide which is complementary and synergistically and

- optionally an emulsifier and / or some alkanolamine

included to protect wood.