DE19802699A1 - Wood preservative with synergistically enhanced activity against basidiomycetes - Google Patents

Abstract

A synergistic combination of copper and/or tin compounds and cyproconazole is used in wood preservatives. Wood preservative contains 2.5-45 wt.% copper and/or tin compound and 0.25-15 wt.% cyproconazole, i.e. (2RS,3RS)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazole-1-yl)b utan-2-ol

Description

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP-A-00 89 958). The effectiveness of these funds in spite of high copper content in the Compared to known copper- and chromate-containing salts with comparable Copper content is not sufficient.

It has now been found that wood preservatives based on copper and / or Tin compounds and cyproconazoles, wherein the content of the metal compound is 2.50 to 45 wt.% and the triazole compound is 0.25 to 15 wt.%, a very good one Possess activity against wood-destroying Basisdiomyceten.

Surprisingly, it was found that for the copper compound and Cypro conazole in this area the fungicidal action is synergistically enhanced and the Mixtures in aqueous wood preservatives are stable on storage. The optimal mix The ratio of metal to cyproconazole is between 1000: 1 and 2: 1, in particular between 500: 1 and 5: 1, preferably 50: 1 and 5: 1, more preferably 25: 1 and 5: 1 parts by weight.

By adding small amounts of organic solvents for wood preservatives medium, z. As alcohols (ethanol, isopropanol), glycols (ethylene glycol, propylene glycol), glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether), glycol ether (butyl glycol), dimethylformamide, N-methylpyrrolidone homogeneous concentrates can be obtained. The solvents additionally act as solubilizers for the triazole. However, with the additional use of acrylic carboxylic acids, cycloalkyl carboxylic acids or aliphatic C ₅ -C ₂₀ mono- or dicarboxylic acids or corresponding amine, alkali or copper salts, the use of solvents can be reduced to a minimum in order to obtain homogeneous concentrates.

The copper compounds can be used as water-insoluble compounds be, for. Copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, Copper fluoride, copper hydroxide carbonate.

An alkanolamine as a further constituent of the wood preservative is in particular Monoethanolamine; the use of other alkanolamines z. For example, isopropanolamine, 1,1-, 1,2-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, Methylethanolamine is possible.

In this case, the amount of alkanolamines added is advantageously such that in the dilute aqueous impregnating solution has a pH of 7 or more, preferably 8.5 to 10.5. The amount of amines should be used for complex formation of copper (1 g atom of copper requires about 4 mol equivalents of amine).

An emulsifier as further constituent of the wood preservative is, for example, an anionic, cationic or nonionic emulsifier or a mixture thereof. Nonionic emulsifiers are z. B. addition products of ethylene oxide (EO) or propylene oxide or mixtures thereof to organic hydroxy compounds, for example, alkylphenols, fatty acids, fatty alcohols and mixtures thereof. As cationic African emulsifiers z. As quaternary ammonium compounds and / or salts of fatty amines (eg., Dimethyl (C ₁₂ -C ₁₄ ) alkylamine) find use.

A quaternary ammonium compound is z. B. a compound according to the general formula

R ¹ R ² R ³ R ⁴ N + Z-

in which
R ^{1 is} an alkyl radical having 8 to 20 carbon atoms, in particular an alkyl radical having 12 to 20 carbon atoms or a benzyl radical which is optionally substituted by C ₁ - to C ₂₀ -alkyl or halogen,
R ^{2 is} C ₁ - to C ₆ -alkyl, C ₃ - to C ₉ -alkoxyalkyl, polymeric ethylene oxide (EO) or propylene oxide with EO or PO n = 2 to 50,
R ^{3 is} C ₁ - to C ₆ -alkyl, C ₃ - to C ₄ -alkoxy, polymeric ethylene oxide (EO) or propylene oxide with EO or PO n = 2 to 50,
R ^{4 is} C ₁ - to C ₂₀ -alkyl or each two of the radicals R ¹ to R ⁴ together with the nitrogen atom form a heterocyclic radical containing 4 to 5 C atoms and one, two or three double bonds, wherein the carbon atoms optionally substituted by C ₁ - to C ₄ -alkyl or halogen and Z is an acid radical, e.g. B. halide means.

As phosphonium compounds, which may additionally be present in the mixture containing triazole compounds and emulsifier, compounds of the formula are particularly suitable

R ¹ ₃ R ² P⁺Y⁻

in the
R ^{1 is} an alkyl radical having 1 to 6 carbon atoms, a hydroxyalkyl radical having 1 to 6 carbon atoms or a phenyl radical,
R ^{2 is} an alkyl radical having 8 to 18 carbon atoms and
Y is an acid radical, in particular a halide anion,
means.

The radicals R ¹ and R ² are preferably straight-chain.

Aliphatic carboxylic acids can improve the homogeneity of the Concentrates are added. Such acids are for. Propionic acid, hexanoic acid,  Heptanoic acid, branched carboxylic acids such. B. 2-ethylene hexanoic acid, isooctanoic acid, Neocarboxylic acids, aliphatic dicarboxylic acids such as. B. sebacic acid, cycloalkyl carboxylic acids such. For example, cyclohexanoic acid, arylcarboxylic acids such as. B. benzoic acid, 3 or 4-hydroxybenzoic acid.

When using the abovementioned acids, it is partly advantageous by addition of complexing, polymeric nitrogen compounds such. B. Polyethylimines to improve the wood preservative penetration in large-scale processes.

Polyethyleneimines (PEI, polymine) are known and are formed by polymerization of 1,2-ethyleneimine. In them, the nitrogen is primary (end group), secondary and tertiary (branching). Suitable polyethylimines with n greater than 10; very good Results are obtained using PEI with a degree of polymerization n between 50 and 1000.

The wood preservatives may optionally contain other compounds, e.g. B. verbin With a fungicidal anion such as a boron compound (eg. 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 Difluorophosphoric acid).

By adding further active ingredients, the range of action of the inventive wood preservative can be optionally improved. Suitable connec tions are z. B. N-Organodiazeniumdioxyverbindungen, organotin compounds, especially tributyl (TBT) tin compounds, isothiazoline compounds of the following formula

R ¹ is hydrogen, an alkyl, alkenyl, alkynyl radical having 1 to 18 carbon atoms, cycloalkyl radical having a C ₃ to C ₆ ring and having up to 12 carbon atoms, an aralkyl or aryl radical having up to 19 carbon atoms,
R ² , R ^{3 are} independently hydrogen, halogen or C ₁ - to C ₄ -alkyl radical or R ² and R ³ part of an aromatic radical.

An addition of other fungicides or insecticides is possible, for. In emulsified form such as N-tridecyl-2,6-dimethylmorpholine (Tridemorph) and / or
4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmorpholine
(Fenpropimorph) and / or chlorinated phenols,
Tetrachlorisophthalsäure-dinitrile,
N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,
N-dimethyl-N'-phenyl- (N-fluoromethylthio) -sulphamide,
N, N-dimethyl-N'-tolyl (N-fluoromethylthio) -sulphamide,
Benzimidazole-2-carbamate methylester,
2-thiocyanomethyl-thiobenzothiazole,
2-Iodbenzoesäureanilid,
1- (1 ', 2', 4'-triazolyl-1 ') - (1- (4'-chlorophenoxy) -3,3-dimethyl-butan-2-one,
1- (1 ', 2', 4'-triazolyl-1 ') - (1- (4'-chlorophenoxy) -3,3-dimethyl-butan-2-ol,
hexachlorocyclohexane,
0,0-diethyl-dithio-phosphoryl-methyl-6-chlorbenoxazolon,
2- (1,3-thiazol-4-yl) -benzimidazole,
N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide,
N- (1,2,2-tetrachloroethylthio) -3,6,7,8-tetrahydrophthalimide,
N-trichloromethylthiophthalimide,
3-iodo-2-propynyl-N-butylcarbamate,
0,0-dimethyl-S- (2-methylamino-2-oxoethyl) -dithiophosphate,
0,0-dimethyl-0- (3,5,6-trichloro-2-pyridyl) thiophosphate,
0,0-dimethyl-S- (N-phthalimido) -methyldithiophosphat,
0,0-dimethyl-O- (α-cyanbenzyliden-amino) -thiophosphate,
6,7,8,9,10-hexachloro, 1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,3,4-benzoedioxo thiepien-3-oxide,
(4-ethoxyphenol) - (dimethyl) - (3- (4-fluoro-3-phenoxy-phenyl) -propyl-silane,
2-sec-butyl-phenyl-N-methylcarbamate,
2-1-propoxyphenyl N-methylcarbamate,
N-methyl-1-naphthyl-carbamate, norbornene-dimethanohexa-chlorocyclosulfite,
1- (4-chlorophenyl) -3- (2,6-di-fluorobenzoyl) -urea,
synthetic pyrethroids, such as (+) - 3- (2,2-dichloro-vinyl-2,2-dimethyl) -cyclopropane-1-carboxylic acid, 3-phenoxybenzyl ester,
3- (2,2-dichloro-vinyl-2,2-dimethyl) -cyclopropane-1-carboxylic acid 3,3-phenoxybenzyl ester,
3- (2,2-dibromovinyl-2,2-dimethyl) -α-cyano-m-phenoxybenzyl-1R, 3R) -cyclopropanecarboxylate (deltamethrin),
α-cyano-3-phenoxybenzyl-isopropyl-2,4-chlorophenylacetate.

The water-dilutable wood preservatives contain - in concentrated form - the Copper is calculated as metal in general, e.g. In an amount of 1.0 to 15.0% (Weight percent).

Suitable concentrates contain z. B.
2.50 to 45%, in particular 10 to 20%, copper compounds,
From 5.00 to 50%, in particular from 20 to 40%, of alkanolamine,
0.25 to 15%, in particular 1 to 10%, triazole compound,
0.5 to 30%, in particular 5 to 15%, of an emulsifier,
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,
0 to 15% of a complex-forming, polymeric nitrogen compound,
wherein the sum each gives 100 wt .-%, and optionally minor amounts of other ingredients, such as. As ammonia, corrosion inhibitors, complexing acids (eg., Nitrilotriacetic acid, ethylenediaminetetraacetic acid when using water with higher degrees of hardness) and, if necessary, water, the proportion of which, however, can be kept low in general and the handling wesent union serves.

However, the invention extends beyond the wood preservatives (concentrates) equally to the dilution of the concentrates with water producible impregnation solutions corresponding to lower individual concentration. The Application concentration is z. B. 0.01 to 1.50 wt .-% metal, for. B. copper, in the aqueous impregnating solution, depending on the type of impregnation and the Degree of danger of the wood to be impregnated.

By dissolving the copper salts, optionally with heat, into the alkanol amines, optionally with addition of acid, water or solvent, and on closing addition of the emulsifier, and the triazole compounds arise high concentrated pastes, liquid concentrates or even two-phase mixtures, the after dilution with water to impregnate wood can. They also give a clear liquid in high concentration in water.

The application of the impregnating solution to protect wood can be done by craft Liche procedures such as spraying, brushing, diving, trough or large technical processes such as boiler pressure, alternating pressure, double Vacuum method done. Under "wood" are both solid wood and To understand wood-based materials such as chipboard, plywood; here may possibly the wood preservative are also incorporated in the glue submerged procedure.

The copper fixation of the wood preservatives of the invention is high when used for Large-scale process is more than 90%.

The concentrates or solutions may be emulsified by water or in water gable dyes and / or pigment preparations are colored.  

An addition of wax, paraffin and / or acrylate dispersions to obtain a water repellent effect or improvement of fixation is possible.

Optionally, the concentrates may also be used in binder-containing water thinnable systems (primers, glazes) are incorporated.

The following examples illustrate the invention.  

Examples

The mixtures of Examples 1 to 3 are prepared by emulsifying Formulation of cyproconazole in an aqueous solution of the metal complex be stirred.

example 1 Concentrate with metal: azole = 25: 1

% w / w Basic copper carbonate 10.9 Monoethanolamines 23.1 Boric acid 16.9 cyproconazole 0.24 Xylene 3.76 Process oil 4.00 Anionic / nonionic emulsifier 1.00 Water 40,10

Example 2 Ready-to-use formulation with metal: azole = 10: 1

% w / w Copper sulphate pentahydrate 1.18 Lactic acid 2.13 Sodium nitrite 1.31 Boric acid 0.79 Ammonium hydroxide 0.57 cyproconazole 0.03 cypermethrin 0.05 Methyl dioxitol 0.64 Anionic / non-ionic emulsifier 0.08 Water 93.22

Example 3 Ready-to-use formulation with metal: azole = 5: 1

% w / w Basic copper carbonate 0.55 Ammonium hydroxide 0.65 Ammonium bicarbonate 0.33 cyproconazole 0.06 Naphtheric acid 0.15 Anionic / nonionic emulsifiers 0.21 Methyl dioxediol 0.48 Water 97.624

Example 4 Ready-to-use formulation with metal: azole = 5: 1

% w / w Copper acetate 0.43 Zinc acetate 0.84 cyproconazole 0.06 Ester alcohol 0.03 2-ethyl hexanoic acid 0.03 Process oil 0.03 Anionic / non-ionic emulsifier 0.06 Water 98.52

concentrates Example 5

% w / w Zinc versatate 15.0 Cyproconzole 0.5 Glycol ether 10.0 White spirit 74.5

Example 6

% w / w Copper caprylates 25.0 Cyproconzole 0.05 Shellsol A 74.75 permethrin 0.2

Example 7

% w / w Copper aypetacs 15.0 Hexylene glycol biborate 10.0 cypermethrin 0.1 cyproconazole 0.1 White spirit 74.8

Example 8

% w / w Zinc octoate 50.0 cyproconazole 1.0 Glycol ether 49.0

Example 9

% w / w Copper versatate 5.0 Cyproconzole 0.01 permethrin 0.1 White spirit 94.89

Example 10

% w / w Monoethanolamines 19.23 Basic copper carbonate 7.27 Benzalkonium chloride (50% active) 8.0 Glyproconazole 0.8 Boric acid 11.3

Claims (1)

Wood preservatives based on copper and / or tin compounds and Cyproconazole, wherein the content of the metal compound is 2.50 to 45% by weight and the triazole compound is 0.25 to 15% by weight.