WO1999037450A1

WO1999037450A1 - Wood preservation agents

Info

Publication number: WO1999037450A1
Application number: PCT/EP1999/000098
Authority: WO
Inventors: Otto Exner; Martin Kugler; Franz Kunisch
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-01-24
Filing date: 1999-01-09
Publication date: 1999-07-29
Also published as: JP2002501034A; PL341904A1; AU2164999A; EP1049573A1; NO20003758L; NO20003758D0; DE19802699A1

Abstract

The invention relates to wood preservation agents containing synergetic amounts of metal compounds and cyproconazole.

Description

1 -

Wood preservative

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP-A-00 89 958). The effectiveness of this

Despite the high copper content, compared to known copper- and chromate-containing salts with a comparable copper content, detergents against wood-destroying basic diomycetes are not sufficient.

It has now been found that wood preservatives based on copper and or

Tin compounds and cyproconazoles, the content of the metal compound being 2.50 to 45% by weight and the triazole compound being 0J5 to 15% by weight, have very good activity against wood-destroying basic diomycetes.

Surprisingly, it was found that the fungicidal action is synergistically enhanced for the copper compound and cyproconazole in this area and the mixtures are stable in storage in aqueous wood preservatives. The optimal mixing 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, particularly preferably 25: 1 and 5: 1 parts by weight.

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 can be obtained. The solvents also act as solubilizers for the triazole. With the additional use of acrylic carboxylic acids, cycloalkkyl carboxylic acids or aliphatic C ₅ -C ₂ mono- or dicarboxylic acids or corresponding amine, alkali or copper salts, the use of solvents can, however, be reduced to a minimum in order to obtain homogeneous concentrates. Water-insoluble compounds can also be used as copper compounds. Preferred copper compounds are copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper chloride, copper fluoride, copper hydroxycarbonate.

Alkanolamines, in particular monoethanolamine, may be mentioned as a further component of the wood preservative. Other alkanolamines are e.g. Isopropanolamine, 1,1-, 1 J-diaminoethanol, aminoethylethanolamine, diethanolamine, triethanolamine, methylethanolamine.

The amount of alkanolamines added is advantageously such that a pH of 7 or more, preferably 8.5 to 10.5, is established in the dilute aqueous impregnation solution. The amount of amines should be sufficient to complex the copper (1 g atom of copper requires approx. 4 mol equivalents of amine).

An emulsifier as a further component of the wood preservative 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 their mixtures with organic hydroxy compounds, for example alkylphenols, fatty acids, fatty alcohols and mixtures thereof. Quaternary ammonium compounds and or salts of fatty amines (such as, for example and preferably, dimethyl (Cj ₂ - Cj) alkylamine) can be used as cationic emulsifiers.

A preferred quaternary ammonium compound is a compound according to the general formula

R! R2R 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 may be substituted by Cp to C ₂ o-alkyl or halogen,

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

R ³ Cp to Cg 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} Cp to C2olkyl or two of the radicals R ¹ to R ⁴ together with the nitrogen atom form a heterocyclic radical which contains 4 to 5 C atoms and one, two or three double bonds, the carbon atoms being optionally by Cp to C ₄ alkyl or halogen are substituted and Z is an acid residue, for example halide.

Compounds of the formula are particularly suitable as phosphonium compounds, which may also be present in the wood preservative

^ RZP ⁺ Y-

in the

R ^{1 is} an alkyl radical with 1 to 6 carbon atoms, a hydroxyalkyl radical with 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 residue, especially a halide anion, - 4 -

means.

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

Aliphatic carboxylic acids can improve the homogeneity of the

Wood preservatives are added. Such acids are exemplary and preferably propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as e.g. 2-ethylene hexanoic acid, isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as e.g. Sebacic acid, cycloalkylcarboxylic acids such as e.g. Cyclohexanoic acid, aryl carboxylic acids such as e.g. Benzoic acid, 3- or 4-hydroxybenzoic acid.

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

Polyethyleneimines (PEI, Polymin) are known and are formed by polymerizing 1 J-ethyleneimine. In them the nitrogen is primary (end group), secondary and tertiary (branching). Polyethylimines 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.

The wood preservatives can optionally contain further compounds, preferably compounds having a fungicidal anion such as a boron compound (alkali borate, amine borate, boric acid, boric acid ester), fluorides (potassium fluoride and or salts of fluoroboric acid and / or fluorophosphoric acid and / or are preferred

Difluorophosphoric acid).

The range of action of the wood preservatives according to the invention is improved by the addition of further fungicides and / or insecticides. Suitable compounds are exemplary and preferably N-organodiazenium dioxy compounds, organotin Compounds, especially tributyl (TBT) tin compounds, isothiazoline compounds of the following formula

R ² χ O f

R ° ^{^} R ¹

in which

R ¹ is hydrogen, an alkyl, alkenyl, alkynyl radical with 1 to 18 carbon atoms, cycloalkyl radical with a C ₃ to Cg 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, are hydrogen, halogen or Cp to C ₄ alkyl or R ² and R ^{3 are} part of an aromatic radical,

N-tridecyl-2,6-dimethylmo holin (tridemorph) and / or

4- (3-para-tertiary-butylphenyl) 2-methyl-propyl-2,6-cis-dimethylmorpholine

(Fenpropimoφh) and / or chlorinated phenols,

Tetrachloroisophthalic acid dinitrile,

N-cyclohexyl-N-methoxy-2,5-dimethyl-foran-3-carboxamide, N-dimethy 1-N '-pheny l- (N-fluoromethyl lthio) sulfamide,

N, N-dimethyl-N'-toluyl (N-fluoromethylthio) sulfamide,

Benzimidazole-2-carbamic acid methyl ester,

2-thiocyanomethyl-thiobenzothiazole,

2-iodobenzoic acid anilide, 1 - (1 ', 4' -triazolyl- 1 ') - (1 - (4' -chlorophenoxy) -3, 3 -dimethylbutan-2-one, l- (rJ ', 4'-triazolyl- l ') - (l- (4'-chlθφhenoxy) -3J-dimethylbutan-2-ol,

Hexachlorocyclohexane,

0,0-diethyl-dithio-phosphoryl-methyl-6-chloroboxazolone,

2- (1,3-thiazol-4-yl) benzimidazole, N-trichloromethylthio-3,6J, 8-tetrahydrophthalimide,

N- (1JJ-tetrachloroethylthio) -3, 6,7,8-tetrahydrophthalimide,

N-trichloromethylthiophthalimide,

3-iodo-2-propynyl-N-butyl carbamate, 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) methyldithiophosphate,

0.0-dimethyl-O- (α-cyanobenzylidene-amino) thiophosphate,

6,7,8,9,10-hexachlor, l, 5,5a, 6,9,9a-hexahydro-6,9-methano-2J, 4-benzoedioxothiepien-3-oxide,

(4-ethoxyphenol) - (dimethyl) - (3- (4-fluoro-3-phenoxyphenyl) propyl silane

2-sec-butyl-phenyl-N-methyl carbamate

2- 1 -propoxyphenyl-N-methyl-carbamate

N-methyl-1-naphthyl-carbamate, norbornene-dimethanohexa-chlorocyclosulfite, 1 - (4-chlorophenyl) -3- (2,6-di-fluorobenzoyl) urea, synthetic pyrethroids, such as

(+) - 3- (2J-dichlorovinyl-2,2-dimethyl) -cyclopropane-l-carboxylic acid-3-phenoxybenzyl ester,

3- (2J-dichlorovinyl-2J-dimethyl) -cyclopropane-1-carboxylic acid-3J-phenoxybenzyl ester,

3- (2J-dibromovinyl-2J-dimethyl) -α-cyano-m-phenoxybenzyl-1 RJR) - cyclopropanecarboxylate (deltamethrin), α-cyano-3-phenoxybenzyl-isopropyl-2,4-chloro-phenyl acetate.

The water-thinnable wood preservatives contain - in concentrated form - that

Copper is generally calculated as metal in an amount of 1.0 to 15.0% (weight percent).

Suitable concentrates preferably contain 2.50 to 45%, in particular 10 to 20%, copper compounds and / or

Tin compounds,

5.00 to 50%, in particular 20 to 40%, alkanolamine,

0J5 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,

the sum being 100% by weight, as well as minor amounts of other components, e.g. 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 can, however, 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 correspondingly lower individual concentration that can be prepared by diluting the concentrates with water. 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.

By dissolving the metal salts, if necessary with the supply of heat, in the alkanolamines, if appropriate with the addition of acid, water or solvent, and then adding the emulsifier, and the triazole compounds, highly concentrated pastes, liquid concentrates or two-phase mixtures are formed, which after dilution with water can be used to impregnate wood. - 8th -

The impregnation solution for the protection of wood can be applied by manual processes such as spraying, brushing, dipping, troughs or by industrial processes such as boiler pressure processes, alternating pressure processes or double vacuum processes. Under "wood" are both solid wood and

Understand wood-based materials such as chipboard, plywood; if necessary, the wood preservative can also be introduced using the glue mixing process.

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 following examples illustrate the invention.

- 9 -

Examples

The mixtures of Examples 1 to 3 are prepared by stirring an emulsified formulation of cyproconazole into an aqueous solution of the metal complex.

example 1

Concentrate with metal: Azole = 25: 1

% w / w

Copper hydroxycarbonate 10.9

Monoethanolamine 23.1

Boric acid 16.9

Cyproconazole 0.24

Xylene 3.76

Process oil 4.00

Anionic / non-ionic emulsifiers 1.00

Water 40.10

Example 2

Ready formulation with metal: Azole = 10: 1

% w / w

Copper sulfate 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 ^ ionogenic emulsifiers 0.08

Water 93.22 - 10 -

Example 3

Ready formulation with metal: Azole = 5: 1

% w / w

Copper hydroxycarbonate 0.55

Ammonium hydroxide 0.65

Ammonium bicarbonate 0.33

Cyproconazole 0.06

Naphthalic acid 0.15

Anionic / non-ionic emulsifiers 0.21

Methyl dioxtiol 0.48

Water 97,624

Example 4

Ready 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 caproic acid 0.03

Process oil 0.03

Anionic / non-ionic emulsifiers 0.06

Water 98.52 - 11 -

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 caprylate 25.0 cyproconazole 0.05

Shellsol A 74.75

Permethrin 0.2

Example 7

% w / w

Kupferaypetacs 15.0

Hexylglycol Biborate 10.0 Cypermethrin 0J Cyproconazole 0J

White spirit 74.8 12 -

Example 8

% w / w

Zinc octanoate 50.0 Cyproconazole 1.0

Glycol ether 49.0

Example 9

% w / w

Copper Versatate 5.0 Cyproconazole 0.01 Permethrin 0.1 White Spirit 94.89

Example 10

% w / w

Monoethanolamines 19.23 copper hydroxycarbonate 1.21

Benzalkonium chloride (50% active) 8.0

Cyproconazole 0.8

Boric acid 11.3

Claims

- 13 patent claims

1. Agents based on copper and / or tin compounds and cyproconazoles, the content of the metal compound being 2.50 to 45% by weight and the triazole compound being 0.25 to 15% by weight.

2. Composition according to claim 1, additionally containing one or more alkanolamines.

3. Composition according to claim 1 or 2, additionally containing one or more

Emulsifiers.

4. Composition according to one of claims 1 to 3, additionally containing one or more further fungicides and / or insecticides.

5. Use of the agent as defined in claims 1 to 4 for protecting wood against microbial attack and destruction.

6. Aqueous impregnation solution for impregnating wood containing an agent according to one of claims 1 to 4.

7. Wood or wood-based materials containing copper and / or tin compounds and cyproconazole.

8. A method for protecting wood from microbial attack and destruction, characterized in that wood or wood-based materials are treated with a copper and / or tin compound and cyproconazole, optionally individually or in combination and, if appropriate, with further auxiliaries and / or active ingredients.