DE3004248A1 - WOOD PROTECTIVE CONCENTRATE AND PRODUCTS MADE THEREOF FOR PRESERVATION OR. PROTECTING WOOD AND WOOD MATERIALS AGAINST WOOD-DESTROYING AND WOOD-MAKING ANIMALS AND VEGETABLE PLANTS - Google Patents

Description

"Wood preservative concentrate and products made from it for .Conservation or protection of wood and wood-based materials towards wood-destroying and wood-discolouring animals and plant pests "

The present invention relates to wood preservative concentrates and agents made therefrom for the preservation or protection of wood and wood-based materials against wood-destroying and wood-discolouring animal and vegetable pests, in particular trunk preservatives and wound treatment agents for trees, based on an organic-chemical, water-insoluble solvent or solvent ; emic, at least one plastic distributed in water and at least one insecticide or insecticide compound soluble in the water-insoluble organic-chemical solvent or solvent mixture and / or at least one fungicide or fun optionally organic dyes. According to the Flrfindunp; consist of inorganic salts and inorganic pimentos free or di ⁿ se compounds only in Oewichtsmen ^ s of less than 2% (based on the wood preservative concentrate) containing HolzsrhutzTittelkonzentrate and derived wood preservative treatment agent, in particular stem retardants and

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Wound treatment agent for trees, made from a water-dilutable Emulsion-dispersion mixture containing certain weight quantities of the organic-chemical water-insoluble solvent or solvent mixture and containing therein at least one insecticide which is soluble in the water-insoluble organochemical solvent or solvent mixture or insecticide mixture and / or at least one soluble in the water-insoluble solvent or solvent mixture Fungicide or fungicide mixture and certain amounts by weight of a water-thinnable plastic dispersion (a), consisting of at least one water-containing and water-thinnable vinyl ester and / or acrylic acid ester and / or Methacrylic acid ester polymer dispersion or co-polymer dispersion, optionally an emulsifier and / or protective colloid and / or wetting agent (b) and optionally water (c) and additionally certain amounts by weight of at least one drying oil (d), preferably a drying oil of vegetable origin.

There are already wood preservatives based on non-volatile, oily or oily organic-chemical Solvents in which at least one organochemical insecticide and / or organochemical fungicide and a Binder, beisDielweise a dissolved synthetic resin, is known (see. DE-OS 27 H 639). Such wood preservatives

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are undiluted, i.e. without the addition of water, on the ho "! 3 applied and point in "! Ute · =? ^ i'ndr» ·] nit-ability in the wood on. The oleic or oleic solvents used in it consist in particular of appropriate mineral oils or derp-n Mix aromatic or mineral oil-based solvents.

It is also from DE-AS I ^ 18 SHf) a method for reducing bearing damage in debarked waste wood, such as crack formation; in drying wood as well as fungal and insect infestation in p; ela °; erted wood, by treating the wood with funcides and / or insects! Zidlösunp; s known where the felled and debarked moist wood is completely treated with an aqueous mixture of a synthetic resin dispersion or emulsion, a pigment reflecting light and heat radiation and a fungicide and insecticide. According to this patent application, the pigment used is preferably finely divided chalk, titanium dioxide or lithopone in weight concentrations of 10 to 50 % by weight , preferably 15 to 25% by weight. Water-soluble fungicides such as borax, boric acid, boron fluoride and df? Oil are used as fungicidal substances. used. The means used within the process cremiiß of DE-AS in 18 846, however, has the disadvantage that it resp. During manufacture. During storage, it can evidently coagulate due to the water-soluble fungicides used, which are strong electrolytes. After all, the remedy is only in a p-learn

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Can be diluted with water to a large extent, since further dilution reduces the effect considerably and the like. occur. In comparative tests, e.g. with commercially available polyvinyl acetate copolymer dispersions, it turns out that unstable emulsions and polymer precipitates have been observed in several cases.

The aim and object of the present invention was to find a means for preserving wood in which the organic-chemical water-insoluble solvent, which is preferably based on petroleum products, in particular corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably White spirit, alkylbenzenes and the like exist, are replaced to a significant percentage by water can, so that the organochemical solvent can be largely saved or reduced in its proportion can and that in addition a plastic dispersion can be used without the risk of precipitation or coagulation or segregation exists during the application process. A segregation or a sediment should thus can largely be avoided when processing the wood preservative. After all, it should Wood preservatives have a good effect. It

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should be stable in storage in the form of concentrates and ready for use at the place of use or at the point of sale Concentration can be diluted by simply adding water. By adhering to certain weight quantities and balanced weight proportions and compositions should be both the concentrate and the water-thinnable Wood preservatives achieve as sufficient a penetration depth as possible in the wood and also as a wound treatment agent be applicable to living trees.

According to the invention, it was found that these objectives are wood preservative concentrates and agents made therefrom for the preservation or protection of wood and wood-based materials against wood-destroying and wood-discolouring animals and plant pests, in particular trunk protection agents and wound treatment agents for trees, based on a organic-chemical water-insoluble solvent or solvent mixture, at least one finely divided in water Plastic and at least one in the water-insoluble organic-chemical solvent or solvent mixture soluble insecticide or insecticide mixture and / or at least one in the water-insoluble organic chemical Solvent or a mixture of solvents containing soluble

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- Ill -

gizid or fungicide mixture, and optionally organic dyes. The wood preservative concentrate according to the invention, free of inorganic salts and inorganic pigments or containing these compounds only in amounts by weight of less than 2% (based on the wood preservative concentrate) consists of a water-dilutable emulsion dispersion mixture which contains 5 to 50% by weight , preferably 35 to 45% by weight ?, of the organochemical water-insoluble solvent or solvent mixture and containing therein at least one insecticide or insecticide mixture soluble in the water-insoluble organochemical solvent or solvent mixture and / or at least one fungicide or fungicide mixture soluble in the water-insoluble solvent or solvent mixture and up to 15 % By weight , preferably 55 to 28% by weight , of a water-thinnable plastic dispersion (a), consisting of at least one water-containing and water-thinnable vinyl ester and / or acrylic acid ester and / or methacrylic acid ester polymer dispersion or cop olymerisatdispersion having a solids content of 35 to 65 wt -.%, preferably 45 to 55 wt .- #, 2 to 0 wt -.% _s preferably 1 to 0.1 wt .- $, of an emulsifier and / or protective colloid and / or a wetting agent (b) and 0 to 20 wt -.%, preferably 2 to l ^l \ wt .-% water (c) and additionally 5 to 15 wt -.% ₃ preferably 7 to 12.9 wt .- # at least one drying

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Oil (d), preferably a drying oil of vegetable origin.

The wood preservative concentrate according to the invention can depending on the place of use, area of use and the like. Be anhydrous or contain an additional amount of water. For the sake of reduction of the transport costs is an anhydrous wood preservative concentrate or a wood preservative concentrate containing only small amounts of water is preferably used. That according to Wood preservative concentrate composed of the invention has the advantage that it can be diluted with water a ready-to-use wood preservative can be produced, which is preferably made of mineral oil or their aromatic fractions or solvent mixtures containing mineral oils such as white spirit and / or alkylbenzenes existing organic-chemical water-insoluble solvents into one a considerable percentage is replaceable by water. This thus increases the proportion of the petroleum-based organic-chemical Solvent largely saved or reduced. Eventually there will be a segregation or a sediment both with the wood preservative concentrate and with the ready-to-use wood preservative and with the Processing of the same largely avoided.

That contained in the agent to dissolve the insecticide

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and / or fungicide used organic-chemical water-insoluble solvent or solvent mixture is a sparingly volatile solvent or solvent mixture with an evaporation number over 55> preferably about 100 j and a flashpoint above 35 ⁰ C, preferably above 55 ⁰ C. This is to oily or oil-type solvents. Corresponding mineral oils or their aromatic fractions or solvent mixtures containing mineral oils, preferably white spirit and / or alkylbenzenes, etc., as well as phthalic acid esters, are used as such solvents. However, by adding a considerable proportion of water to the wood preservative concentrate, the content of such petroleum products in the ready-to-use wood preservative is considerably reduced.

The water-insoluble j in the solvent or solvent mixture dissolved insecticide and / or fungicide or insecticide and / or fungicide mixture is in amounts by weight of 2 to 25% by weight, preferably 3 to 20% by weight, in the concentrate contain.

Insecticides or insecticide mixtures used are those which are soluble in the organic chemical solvent or solvent mixture used are. Carbamates, phosphoric acid esters,

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Thiophosphoric acid ester, dithiophosphoric acid ester or thionophosphoric acid ester, Dieldrin, aldrin, lindane or other insecticidal chlorinated hydrocarbons, pyrethroids such as allethrin, cyclethrin, purethrin, tetramethrin, resmethrin and bioresmethrin etc. as well as endosulfan for use or mixtures of two or more of these compounds.

As insecticidal thionophosphoric acid esters, halogenated or halogen-free thionophosphoric acid esters are preferred the formula

C ₂ H ₅ O

preferably (diethoxy-thiophosphoryloxyimino) -phenylacetonitrile or 0,0-diethyl-O- («t -cyanbenzylidene-aminoithionophosphate and / or (diethoxythiophosphoryloxyimino) -2-chlorophenylacetonitrile used.

The preferred insecticidal carbamates which are soluble in the water-insoluble organic-chemical solvents are used Alkoxyphenyl-N-alkylcarbamates of the general formula

{>^'V -0-C-NH-R ₁ 0-R ₂

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and / or an alkylphenyl-N-alkylcarbamate of the general formula

// VOC-NH-R ₁ ^ R ₂

wherein in each case for R ^ an alkyl radical with 1-4 C atoms, preferably is a methyl radical and R ^ is an alkyl radical with 1-5 carbon atoms, preferably an alkyl radical with 3 or 4 C atoms, for use.

The fungicides or fungicide mixtures used are those which are used in the organic-chemical Solvent or solvent mixture are soluble. Preference is given to tetravalent organotin compounds, chlorinated phenols (preferably penta- or tetrachlorophenol), fungicidal 1-trityl-1,2,4-triazoles of the general formula

N

Il

Marg

in which R represents a fluorine, chlorine or bromine atom, a trifluoromethyl, nitro or cyano group or an alkyl

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group with up to ¹ J carbon atoms, and η represents the numbers 1 or 2, and the salts of organic or inorganic acids, fungicidal salts of N-nitroso-N-cyclohexylhydroxylamins or tris (N-cyclohexyl-diazeniumdioxy) metal compound, preferably Aluminum compound, and / or Ν, Ν-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) sulfamide and / or NjN-dimethyl-N'-p-tolyl-N'-Cdichlorofluoromethylthio) sulfamide or mixtures of two or several of these connections are used.

As oil-soluble, tetravalent, fungicidal organotin compounds The following can be used, for example: bis (tri-butyltin) oxide, tributyltin benzoate, tri-nbutyltin-8-oxyquinoline, Tributyl tin phosphate.

The fungicides used can also be replaced in whole or in part by fungicidal oil-soluble compounds or derivatives or mixtures of chlorophenols, preferably compounds or mixtures of penta- and / or tetrachlorophenol with low-volatility amines, for example dehydroabietylamine, Ν, Ν-dimethyl-N'-phenyl -N ¹ - (fluorodichloromethylthio) sulfamide and Ν, Ν-dimethyl-N'-p-tolyl-N '- (dichlorofluoromethylthio) -sulfamide, zinc (N, N-ethylene-bis- (dithiocarbamide), zinc (N, N-dimethyldithiocarbamate), tetramethylthiouram disulfide and / or N-cyclohexy1-N-methoxy-2,5-dimethy1-furan-3-carbonaureamide

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Furthermore, in combination with the aforementioned fungicides, the organic phosphoric acid esters of the general formula

1

wherein R is an alkyl group having 1 to 4 carbon atoms, R a saturated or unsaturated alkyl group having 1 to 4 carbon atoms or a group of the formula

R ^ -O-CH ₂ CH ₂ -

in which R- ^ is an alkyl group with 1 to 4 carbon atoms, X is a hydrogen or a halogen atom and η is 1, 2 or 3

and or

N- (dimethylaminomethylidene) thiol (thiono) phosphoric acid

esterimide of the formula
RS. X

, "PN = CH-N
R'O '

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in which X represents an oxygen or sulfur atom, R ^{1 represents} an alkyl radical with 1 to 6 carbon atoms and R represents an alkyl, alkenyl, alkynyl, aralkyl, alkylthioalkyl or alkenylthialkyl radical,

and or

5-imino-l, 2, ^4-i-triazine derivatives of general formula

in which η is O or 1, R _{1 is} alkyl having 1 to 4 carbon atoms or amino, Rp is alkyl having 1 to * J carbon atoms and X is oxygen, sulfur or the -NH- group.

The emulsifier used is an ethoxylated phenol and / or an ethoxylated alkyl, aryl, arylalkylphenol or a or ethoxylated phenol containing several other side groups and / or an ethoxylated organic acid, preferably an ethoxylated nonylphenol and / or an ethoxylated fatty acid are used. Likewise, protective colloids and / or

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Wetting agent as a complete or partial replacement of the emulsifier Find use. In combination of the selected composition, the emulsifier or emulsifier mixture and the specified weight ratios, the penetration capacity of the active ingredients in the wood is promoted.

According to an expedient embodiment, the drying Oil (d) completely or partially replaced by a water-thinnable alkyd resin dissolved in an organochemical water-soluble solvent.

This embodiment makes it possible to reduce or replace the proportion of drying oil. The drying oil (based on the total amount of drying oil in the wood preservative concentrate equal to 100 %) is expediently mixed with up to 65 %, preferably up to 35 %, by an alkyd resin that is dilutable in an organic-chemical water-soluble solvent.

At least one water-soluble polyol is used as the organochemical water-soluble solvent for the alkyd resin .

The organic-chemical water-soluble solvent for the alkyd resin is preferably a water-soluble glycol, for example

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300A2A8

wise ethylene or butyl glycol or another water-soluble alkylene glycol or one of their water-soluble derivatives .

For producing the ready-treating agent and wood preservative is added to the concentrate in a ratio of concentrate: water of 1: 1 to 1: 4, preferably 1: 1.5 to 1: 3 ₃ added water.

The invention further relates to a method for producing the wood preservative concentrate and the agents for preserving and protecting wood and wood-based materials produced therefrom. The wood preservative concentrates are prepared by chemical organic-in, poorly volatile, oily or oil-like solvent or solvent mixture and the drying oil the water-insoluble insecticides or insecticide mixtures and / or water insoluble fungicides or fungicide mixtures at temperatures of - 5 ⁰ C to +80 ⁰ C , preferably from 15 ⁰ C to 45 ⁰ C, and at pressures of 400 mm Hg to 850 mm Hg (0.5332 to 1.1332 bar), preferably 6OO mm Hg to 790 mm Ho; (0.7999 to 1.0532 bar), are treated as long as until a solution is formed, and then this solution in a water-dilutable vinyl ester and / or acrylic ester and / or Methacrylsäureesterpolymerisat- or -copolymerisatdispersion at temperatures below 50 ⁰ C, preferably at tem-

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temperatures between 15 and 45 ⁰ C _{5 is} emulsified with stirring. By diluting the concentrate with water in a ratio of 1: 1 to 1: 4, preferably 1: 1.5 to 1: 3, the ready-to-use agent for preserving or protecting wood and wood-based materials against wood-destroying and wood-discoloring animal and plant pests, in particular Trunk preservatives and wound treatment agents for trees.

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Examples of wood preservative concentrates:

example 1 MO, - Weight Commercially available styrene-acrylate 12, - Weight Dispersion (50 #) (Acronal 290 D) 13, - Weight Phthalic acid ester 18, - Weight Linseed oil *, - Weight Tetrachlorophenol 13.- Weight Aldrin water

Example 2

Commercially available homopolymeric poly

vinyl acetate dispersion (50 # ig) (Mowilith DC) k2 - wt%.

Phthalic acid 12 - wt% Water-dilutable, medium oil ^+.

Alkyd resin 10 - wt%.

Tetrachlorophenol 20 - wt%.

Aldrin 3, - wt%.

Water 13 - wt%.

+ Water-thinnable, medium-oil alkyd resin based on drying Vegetable fatty acids with an oil content / triglyceride of about £ 50 and phthalic anhydride of about $ 21.

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Example 3

Commercially available styrene-acrylate

Dispersion (50 # ig) (Acronal 290 D) 50 - wt%.

Diazenium-dioxy-salt of aluminum 4, - wt. %

Lindane 2.6 wt. %

Phthalic acid 10 - wt%.

Linseed oil 10 -% by weight aromatic hydrocarbon.
(Flmp. According to DIN 51755: 63 ⁰ C;

Evaporation rate: 148) 9.4 wt. %

Water 14 - wt%.

Example 4

Commercially available homopolymer polyvinyl

acetate dispersion (50 # ig) (Mowilith DC) 46, - wt. %

Safflower oil 12 - wt%.

Phthalic acid 12 - wt%.

Diazenium-dioxy-salt of aluminum 4, - wt. %

Lindane 2.5 wt. %

Aromatic hydrocarbon

(Point according to DIN 51755: 63 ⁰ C;

Evaporation rate: 148) 9.5% by weight.

Water 14 - wt%.

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Claims (9)

Patent claims: 1 / Wood preservative concentrate and agents made from it for the preservation or protection of wood and wood-based materials against wood-destroying and wood-discolouring animal and vegetable pests, in particular trunk preservatives and wound treatment agents for Bourne, based on an organic-chemical water-insoluble solvent or solvent mixture, at least one plastic finely dispersed in water and at least one insecticide or insecticide mixture soluble in the water-insoluble organic-chemical solvent or solvent mixture and / or at least one fungicide or fungicide mixture soluble in the water-insoluble organic-chemical solvent or solvent mixture, and optionally organic dyes, characterized in that the inorganic salts and of Inorganic pigments or hol containing these compounds only in amounts by weight of less than 2% (based on the wood preservative concentrate) zprotective agent concentrate and wood-protecting treatment agents made therefrom, in particular trunk preservatives and wound treatment agents for trees, consists of a water-thinnable emulsion-dispersion mixture which 130033/0251 5 to 50 lew. -%, preferably 35 to 45 wt. -35, of the organic-chemical water-insoluble solvent or solvent mixture and containing therein at least one, in the water-insoluble organochemical Solvent or solvent mixture soluble insecticide or insecticide geraisch and / or at least one in the water-insoluble solvent or solvent mixture soluble fungicide or fungicide mixture and 88 to 15 wt .-%, preferably 55 to 28 wt .- %, a water-thinnable plastic dispersion (a), consisting from at least one water-containing and water-thinnable vinyl ester and / or acrylic acid ester and / or methacrylate polymer dispersion or copolymer dispersion with a solids content of 35 to 65% by weight, preferably 45 to 55% by weight , 130033/0251 BATH ORIGINAL 2 to 0% by weight , preferably 1 to 0.1% by weight , an emulsifier ?, and / or protective colloid and / or a wetting agent (b) and 0 to 20% by weight , preferably 2 to 14 wt. Water (c) as well as additionally 5 to 15% by weight , preferably 7 to 12.9% by weight, contains at least one drying oil (d), preferably a drying oil of vegetable origin 130033/0251 BATHROOM OB 2. Wood preservative concentrate and wood-protecting treatment agent prepared therefrom according to claim 1, characterized in that the organic-chemical water-insoluble solvent or solvent used to dissolve the insecticide and / or fungicide contained in the agent or solvent; smittel ^ emisch a low volatility, it is solvent with an evaporation number over 55 », preferably over 100, and a flash point over 35 ⁰ C, preferably over 55 ⁰ C. 3. Wood preservative concentrate and wood preservatives made from it Treatment agent according to claims 1 and 2, characterized in that the water-insoluble, im Solvent or Solvent F. Mixed Insecticide and / or fungicide or insecticide and / or fungicide mixture in weights of 2 to 25% by weight _} preferably 3 to 20% by weight , is contained in the concentrate. 130033/0251 / ~ \ η.ί / "ν IKI Al ~ 5 - 4. Wood preservative concentrate and wood preservative Pehandlun ^ s means produced therefrom according to speeches 1 to 3, characterized in that the insecticide or insecticide is a mixture of a carbamate, a phosphoric acid ester, a phosphoric acid ester, a thiophosphoric acid ester, a dithiophosphoric acid ester or a thionophosphoric acid ester! chlorinated hydrocarbon, ^ inem pyrethroid and / or from endosulfan or from two or more ^Q n this Vr>rhindunp; e ⁿ b ^ st ^ ht. 5. ^u ol zsrihut ", mitt" l ¹ - <O »T ^ entr3.t and wood-protecting treatment agents produced therefrom according to claims 1 to 4, characterized in that the fungicide or funojicide f ^ emic of a tetravalsnten zinnor. ^ Anic compound ·, A ^ m chlorinated phenol, preferably penta- or tetrachlorophenol, a l- ^ rityl -! ^, ^ - triazole of the general formula 130033/0251 BATH ORIGINAL in which R stands for a fluorine, chlorine or bromine atom, a trifluoromethyl, nitro or cyano runpe or an alkyl run with up to 4 carbon atoms and η stands for d: e numbers 1 or 2, as well as their salts of organic or inorganic Acids, a salt of N-nitroso-N-cyclohexylhydroxylamine or tris (N-cyclohexyl-diazeniumdioxy) metal compound, preferably aluminum compound, and / or N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethyl) sulfamide and / or N ₃ N-dimethyl-N'-p-tolyl-N '- (dichlorofluoromethylthio) sulfamide, or consists of two or more of these compounds. 6. Wood preservative concentrate and wood preservatives made from it Treatment agent according to one or more of claims 1 to 5, characterized in that the drying oil (d) in whole or in part by one in an organic chemical water-soluble solvent dissolved water-thinnable alkyd resin is replaced. 7. Wood preservative concentrate and wood preservatives made from it Treatment agent according to Claims 1 to 6, characterized in that daP> the organic chemical water-soluble Solvent for the alkyd resin at least one 130033/0251 BATH ORIGINAL water-soluble polydl, preferably a glycol. 8. Wood preservative concentrate and wood preservative treatment agents made from it according to requirements 1 to 7, characterized in that the ready-to-use Treatment agent from the wood preservative concentrate and water in the ratio of concentrate: water such as 1: 1 to 1: 4, preferably 1: 1.5 to 1: 3. 9. Process for the production of the wood preservative concentrate and the wood preservative treatment agent according to one or more of claims 1 to 8, characterized in that in the organochemical, non-volatile, oily or oil-like solvent or Solvent mixture and the drying oils the water-insoluble insecticides or insecticide mixtures and / or water-insoluble fungicides or fungicide mixtures at temperatures of - 5 ⁰ ^ to +80 C, preferably 15 ⁰ C to 45 ° C, and when you press 400 mm Hg to 850 mm Hg (0.5332 to 1.1332 bar) preferably 600 mm Hg to 7 <30 mm Hg (0.7999 to 1.0532 bar), 130033/0251 BATH be treated until a solution is formed and then this solution into a water-dilutable
Vinyl ester and / or acrylic ester and / or Methacrylsäureesterpolymerisat- or -copolymerisatdisnersion at temperatures below 50 ⁰ C, at vorzupjsweise
Temperatures between 15 and 45 ° Π, with stirring, is reduced. 130033/0251