JP2002501034A - Wood preservative - Google Patents

Abstract

  (57) [Summary] The present invention relates to a wood preservative containing a synergistic effect of a metal compound and cyproconazole.

Description

DETAILED DESCRIPTION OF THE INVENTION

Wood preservatives based on inorganic copper compounds with alkanolamines as complexing agents are known (EP-A-0089 958). The activity of these agents against wood-destroying basidiomycetes is inadequate compared to known copper and chromate containing salts which have comparable copper content despite high copper content.

A wood preservative based on a copper and / or tin compound and cyproconazole, wherein the content of the metal compound is 2.50 to 45% by weight and the content of the triazole compound is 0.25% Wood preservatives, which have been found to have very good activity against wood-destroying basidiomycetes.

Surprisingly, it has been found that for this range of copper compounds and cyproconazole, the bactericidal action is synergistically enhanced and this mixture has a long storage stability in aqueous wood preservatives. Was done. The optimal mixing ratio of metal to cyproconazole is between 1000: 1 and 2: 1 by weight, especially between 500: 1 and 5: 1, preferably between 50: 1 and 5: 1, particularly preferred. Is between 25: 1 and 5: 1.

[0004] Wood preservatives contain small amounts of organic solvents such as alcohols (ethanol or isopropanol), glycols (ethylene glycol or propylene glycol),
A homogeneous concentrate can be obtained by adding glycol ether (ethylene glycol monomethyl ether or ethylene glycol monoethyl ether), glycol ether ester (butyl glycol acetate), dimethylformamide or N-methylpyrrolidone. These solvents additionally act as solubilizers for the triazole. However, aryl carboxylic acids, cycloalkyl carboxylic acids or aliphatic C ₅ -C ₂₀ - mono - or dicarboxylic acid or the corresponding amine, by additional use of alkali metal or copper salt, to obtain a homogeneous concentrate Solvent use can be reduced to a minimum.

[0005] The copper compound used may also be a water-insoluble compound. Preferred copper compounds are copper sulfate, copper acetate, copper hydroxide, copper oxide, copper borate, copper chloride, copper fluoride or basic copper carbonate.

[0006] Alkanolamines, especially monoethanolamine, are mentioned as further components of wood preservatives. Other alkanolamines are, for example, isopropanolamine, 1,1- and 1,2-diaminoethanol, aminoethylethanolamine,
Diethanolamine, triethanolamine and methylethanolamine.

Here, the addition amount of the alkanolamine is advantageously such that a dilute aqueous impregnation liquid gives a pH of 7 or more, preferably 8.5 to 10.5. The amount of amine must be sufficient to complex copper (1 g-atom of copper requires about 4 molar equivalents of amine).

[0008] As a further component of the wood preservative, the emulsifier is, for example, an anionic, cationic or nonionic emulsifier or a mixture thereof. Nonionic emulsifiers are, for example, adducts of ethylene oxide (EO) or propylene oxide or mixtures thereof with organic hydroxy compounds, such as alkylphenols, fatty acids, fatty alcohols and mixtures thereof. Examples of suitable cationic emulsifiers are quaternary ammonium compounds and / or fatty amines (e.g., and preferably, dimethyl - (C ₁₂ -C ₁₄₎ - alkyl amines, etc.) it is a salt of.

Preferred quaternary ammonium compounds have the general formula R ¹ R ² R ³ R ⁴ N ⁺ Z ⁻ , wherein R ¹ is alkyl of 8 to 20 carbon atoms, in particular of 12 to 20 carbon atoms. R ² is C ₁ -C ₆ -alkyl, C ₃ -C ₉ -alkoxyalkyl or EO or PO units, alkyl or unsubstituted or benzyl substituted by C ₁ -C ₂₀ -alkyl or halogen. Is a polymer ethylene oxide (EO) or propylene oxide (PO) wherein n is from 2 to 50, and R ³ is C ₁ -C ₆ -alkyl, C ₃ -or C ₄ -alkoxy or EO properly is an ethylene oxide polymer is a 50 number of n is from 2 PO units (EO) or propylene oxide (PO), and R ⁴ is, C ₁ -C ₂₀ - Al A le, or two R ⁴ groups from R ¹ together with the nitrogen atom, form a heterocyclic group containing 4 or 5 carbon atoms, and two or three double bonds, carbon The atoms are unsubstituted or substituted by C ₁ -C ₄ -alkyl or halogen, and Z is an acid group, for example a halide.

[0010] Particularly suitable phosphonium compounds which may be included in the wood preservative has the general formula _{^{R 1 3 R 2 P + Y}} - ( wherein, R ¹ is alkyl of 1 to 6 carbon atoms, from 1 A hydroxyalkyl or phenyl of 6 carbon atoms, R ² is alkyl of 8 to 18 carbon atoms, and Y is an acid group, especially a halide anion.

R ¹ and R ² are preferably straight-chain.

[0012] Aliphatic carboxylic acids can be added to improve the uniformity of the wood preservative. Examples of such acids are preferably propionic acid, hexanoic acid, heptanoic acid, branched carboxylic acids such as 2-ethylenehexanoic acid or isooctanoic acid, neocarboxylic acids, aliphatic dicarboxylic acids such as sebacic acid, cyclohexane Alkyl carboxylic acids, for example, cyclohexanoic acid, and aryl carboxylic acids, for example, benzoic acid or 3- or 4-hydroxybenzoic acid.

When using the above-mentioned acids, in large-scale industrial processes, the addition of complexing polymeric nitrogen compounds, for example polyethyleneimine,
It would be advantageous if there were to improve the penetration of wood preservatives.

[0014] Polyethyleneimine (PEI, polymine) is known and is produced by the polymerization of 1,2-ethyleneimine. This is primary (terminal group), secondary or tertiary (branched)
Contains nitrogen in the form of Polyethyleneimines where n is greater than 10 are preferred.
Very good results are obtained when using PEI having a degree of polymerization n between 50 and 1,000.

If necessary, the wood preservatives may comprise further compounds, preferably boron compounds (preferably alkali metal borates, amino borates, boric acid and borate esters) and fluorides (potassium fluoride and / or fluoroboric acid and (Preferably fluorophosphoric acid and / or difluorophosphoric acid).

The spectrum of action of the new wood preservatives is improved by adding further fungicides and / or pesticides. Examples of suitable compounds are preferably N-organodiazenium dioxy compounds, organotin compounds, especially tributyltin (TB
T) Compound and the following formula

[0017]

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Wherein R ¹ is hydrogen, an alkyl, alkenyl or alkynyl group of 1 to 18 carbon atoms, a C ₃ -C ₆ -ring and cycloalkyl having up to 12 carbon atoms or An aralkyl or aryl group having not more than 2 carbon atoms, and R ² and R ³ independently of one another are hydrogen, halogen or C ₁ -C ₄ -alkyl, or R ² and R ³ are aromatic groups Is an isothiazoline compound).

N-tridecyl-2,6-dimethylmorpholine (tridemorph) and / or 4- (3-para-t-butylphenyl) -2-methyl-propyl-2,6-cis-dimethylmorpholine (Fenpropimorph) (fe
npropimorph) and / or chlorinated phenol, tetrachloroisophthalodinitrile, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, N-dimethyl-N'-phenyl- (N- Fluoromethylthio) sulfamide, N, N-dimethyl-N′-toluyl- (N-fluoromethylthio) sulfamide, methylbenzimidazole-2-carbamate, 2
-Thiocyanomethylthiobenzothiazole, 2-iodobenzanilide, 1- (
1 ', 2', 4'-Triazol-1'-yl) -1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-one, 1- (1 ', 2', 4'- Triazol-1'-yl) -1- (4'-chlorophenoxy) -3,3-dimethylbutan-2-ol, hexachlorocyclohexane, O, O-diethyldithiophosphorylmethyl-6-chlorobenzooxazolone, 2- ( 1,3-thiazole-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, O, O-dimethyl S- (2-methylamino-2-oxaethyl) dithiophosphate, O, O-
Dimethyl O- (3,5,6-trichloro-2-pyridyl) thiophosphate, O
, O-dimethyl S- (N-phthalimido) -methyldithiophosphate, O, O
-Dimethyl O- (α-cyanobenzylideneamino) thiophosphate, 6,7,
8,9,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6
, 9-Methano-2,3,4-benzoedioxothiepiene 3-oxide, (4
-Ethoxyphenol)-(dimethyl) -3- (4-fluoro-3-phenoxyphenyl) propylsilane, 2-s-butyl-phenyl N-methylcarbamate, 2-1-propoxyphenyl N-methylcarbamate, 1-naphthyl N-methyl carbamate, norbornene dimethanohexachlorocyclosulfite, 1-
(4-chlorophenyl) -3- (2,6-difluorobenzoyl) -urea; 3
-Phenoxybenzyl (+)-3- (2,2-dichlorovinyl-2,2-dimethyl) -cyclopropane-1-carboxylate, 3,3-phenoxybenzyl 3
-(2,2-dichlorovinyl-2,2-dimethyl) -cyclopropane-1-carboxylate, 3- (2,2-dibromovinyl-2,2-dimethyl) -α-cyano-m-phenoxybenzyl ( 1R, 3R) -cyclopropanecarboxylate (deltamethrin), α-cyano-3phenoxybenzylisopropyl-2,4
Synthetic pyrethroids such as chlorophenyl acetate;

In the concentrated form, the water-dilutable wood preservative generally contains an amount of 1.0 to 15.0% by weight of copper, calculated as metal.

Suitable concentrates are preferably 2.50 to 45%, in particular 10 to 20%, of copper and / or tin compounds, 5.00 to 50%, especially 20 to 40% of alkanolamines, 0. 25 to 15%, especially 1 to 10%, of the triazole compound;
0.5 to 30%, in particular 5 to 15%, of emulsifiers, 0 to 40% of compounds having fungicidal inorganic or organic anions, 0 to 40% of organic solvents, 0 to 40% of aliphatic mono- or dicarboxylic acids It contains acids and / or cycloalkyl carboxylic acids and / or cycloaryl carboxylic acids and from 0 to 15% of complexing polymerized nitrogen compounds, the sum in each case being 100% by weight and, if necessary, small amounts Other components such as ammonia, corrosion inhibitors, complexing acids (eg, nitrilotriacetic acid or ethylenediaminetetraacetic acid when using water of relatively high hardness) and, if necessary, generally in small amounts. It contains water in an amount that is stopped and basically serves the purpose of handling.

In addition to wood preservatives (concentrates), the present invention also relates to corresponding individual low-concentration impregnating liquids which can be produced by diluting the concentrate with water. The treatment concentration corresponds to, for example, 0.01 to 1.50% by weight of a metal, for example copper, in an aqueous impregnation liquid, depending on the impregnation method and the degree of risk that the wood to be impregnated is exposed.

With heating, if necessary, with or without the addition of acid, water or solvent,
Upon dissolution of the metal salt in the alkanolamine, followed by the addition of emulsifiers and triazole compounds, a thick paste, liquid concentrate or two-phase mixture is formed, which can be used to impregnate wood after dilution with water. it can.

[0024] The impregnating liquid is stored in the wood by a manual method such as spraying, brushing, dipping or bath impregnation, or by a large-scale industrial process such as a pressurized process, an alternating pressurized process or a double vacuum process. Can be used for Wood is understood to refer to solid wood and woodworking materials such as particle board or plywood. In this case, a wood preservative may also be introduced in the adhesive mixing step.

The degree of fixation of copper in this new preservative is high, when using large-scale industrial methods, more than 90%.

The concentrate or liquid can be colored with a water-soluble or water-emulsifiable dye and / or pigment preparation.

To obtain a water-repellent effect or to improve the fixation, wax, paraffin and / or acrylate dispersions are added.

If desired, the concentrate can also be included in a binder-containing water-dilutable system (primer or clear coat).

The following examples illustrate the invention.

[0030]

【Example】

The mixtures of Examples 1 to 3 are produced by adding an emulsified preparation of cyproconazole to an aqueous solution of a metal complex and stirring.

Example 1 Metal: Azole = 25: 1 Concentrate% w / w Basic Copper Carbonate 10.9 Monoethanolamine 23.1 Boric Acid 16.9 Cyproconazole 0.24 Xylene 3.76 Process Oil 4.00 anion / nonionic emulsifier 1.00 water 40.10 Example 2 metal: azole = 10: 1 finish formulation% w / w copper sulfate pentahydrate 1.18 lactic acid 2.13 sodium nitrite 1. 31 Boric acid 0.79 Ammonium hydroxide 0.57 Ciproconazole 0.03 Cypermethrin 0.05 Methyl dioxitol 0.64 Anion / nonionic emulsifier 0.08 Water 93.22 Example 3 Metal: azole = 5: 1 finish formulation% w / w basic copper carbonate 0.55 ammonium hydroxide Beam 0.65 bicarbonate of ammonium 0.33 cyproconazole 0.06 naphthalate 0.15 anionic / nonionic emulsifiers 0.21 Methyl dioxy tall 0.48 Water 97.624 Example 4 Metal: azole = 5: 1 Finished formulation% w / w Copper acetate 0.43 Zinc acetate 0.84 Ciproconazole 0.06 Ester alcohol 0.03 2-Ethyl caproic acid 0.03 Process oil 0.06 Anion / nonionic emulsifier 0.06 Water 98 0.52 Concentrate Example 5 % w / w Zinc Versate 15.0 Ciproconazole 0.5 Glycol Ether 10.0 Mineral Spirit 74.5 Example 6 % w / w Copper Caprylate 25.0 Ciproconazole 0.0 05 Shellsol A 74.75 permethrin 0.2 example 7% w / w copper Aipetakkusu ( ypetacs) 15.0 hexyl glycol vivo rate 10.0 cypermethrin 0.1 cyproconazole 0.1 mineral spirits 74.8 Example 8% w / w octanoic acid zinc 50.0 cyproconazole 1.0 glycol ether 49. 0 Example 9 % w / w Copper Versatate 5.0 Ciproconazole 0.01 Permethrin 0.1 Mineral Spirit 94.89 Example 10 % w / w Monoethanolamine 19.23 Basic Copper Carbonate 7.27 Benza Chloride Ruconium (50% active) 8.0 Cyproconazole 0.8 Boric acid 11.3

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Kuniche, Franz Deutsche D-51519 Odenthal Amue Allen felt 3 F term (reference) 2B230 AA01 BA01 BA17 CA06 CA30 CB10 CC04 CC05 CC30 DA02 EB01 4H011 AA01 AC01 BA01 BA06 BB04 BB09 BB15 BB18 BC01 BC03 BC04 BC06 BC18 BC20 DA15 DA16

Claims (8)

[Claims] 1. A copper compound and / or a tin compound and cyproconazole (cyproconazole).
Conazole) -based compositions having a metal compound content of 2.50 to 45% by weight and a triazole compound content of 0.25 to 15% by weight. 2. The composition according to claim 1, which additionally contains one or more alkanolamines. 3. The composition according to claim 1, which additionally comprises one or more emulsifiers. 4. The composition according to claim 1, which additionally comprises one or more further fungicides and / or insecticides. 5. Use of the composition according to claims 1 to 4 for preserving wood from microbial attack and destruction. 6. An aqueous impregnating liquid for impregnating wood, comprising the composition according to claim 1. 7. A wood or wood material containing a copper compound and / or a tin compound and cyproconazole. 8. The wood or wood material is treated with a copper compound and / or a tin compound and cyproconazole, optionally individually or in combination, and optionally, with further auxiliaries and / or active ingredients. A method for preserving wood from microbial attack and destruction.