DD247176A1 - WOOD PRESERVATIVES - Google Patents

Abstract

Wood preservatives in dispersion form based on water-soluble and wasserunloeslicher active substances for the protection of wood and wood-based materials against infestation and destruction by microorganisms and insects. It is a wood preservative based on Wasserloeslicher ammonium compounds and wasserunloeslicher agents with improved Auswaschbestaendigkeit be developed with relatively little drug use. The inventive wood preservative contains 65 to 89.2 wt .-% of a compound R4-N-R2 X, 0.05 up to 10 wt .-% of active ingredients based on organotin compounds and / or halogenated organic compounds, 0.1 to 10 wt .-% of the reaction product of a mono- to polychlorinated hydrocarbon having up to 20 carbon atoms with a dialkylamine, 0.1 to 15 wt .-% of a compound of the general formula R4-N-R5-N-R4 XY2wobei this component in a ratio of 0.1 to 4 to the weight ratio of the active ingredient based on organotin compounds and / or in a ratio of 0.1 to 8 to the weight ratio of the active ingredient based on the halogenated organic compounds and the active ingredients optionally using 0.1 to 5 wt. %, of a non-ionic surfactant are dissolved or dispersed in water and the dispersion optionally contains 0.1 to 2 wt .-% of a corrosion inhibiting agent.

Description

CH ₃ COO

consists.

4. Wood preservative according to item 1, characterized in that as organotin compounds bis-tri-n-butyltin oxide, tri-n-butyltin acetate, tri-n-butyltin phosphate, tri-n-butyltin chloride are used individually or in admixture.

5. Wood preservative according to item 1, characterized in that are used as halogenated ^ organic compounds pentachlorophenol, dichlorodiphenyltrichloromethylmethane, γ-hexachlorocyclohexane, individually or in a mixture.

6. Wood preservative according to item 1, characterized in that the water-soluble active ingredients are dissolved in water and the water-insoluble active ingredients in diesel oil and the latter is dispersed in the solution of the water-soluble active ingredients.

7. Wood preservative according to item 1, characterized in that the water-insoluble active ingredients are dissolved in diesel oils and the water-soluble active ingredients dissolved in water are dispersed in the diesel oil.

Field of application of the invention

The invention relates to wood preservatives in dispersion form based on water-soluble and water-insoluble active substances for the protection of wood and wood-based materials against infestation and destruction by microorganisms and insects.

Characteristic of the known technical solutions

A process is known for the permanent preservation of wood by impregnation with a fungicidal and insecticidal wood preservative on an amine basis, whereby as impregnating agent aqueous solutions of compounds of the general formula

-C-O if 0

H-

W-CH

wherein R _{1 is} a hydrogen atom or an alkyl radical having 1 or 2 C atoms or a radical of the general formula

- (CH

I!

C-)

H-U-CH-I

with η = O to 4, R _{2 is} an alkyl radical having an average chain length of 15 carbon atoms, are used, which optionally contain a corrosion inhibiting agent (DE-AS 1299405).

A disadvantage of this process is a relatively low biocidal activity and washout resistance of the compounds mentioned in the wood body to be observed. As a result, with this method, only a relatively short period of protection of wood and wood-based materials from infestation of wood-discoloring and -destructive fungi and insects can be achieved.

There are often higher concentrations of active ingredient required, which results in a further disadvantage, a greater health risk to the user.

Also known is an aqueous agent in dispersion form for treating timber, which contains from 0.01 to 2% by weight of a compound of the general formula

- R

R R or R - R - Y R \ I I Sn-X sn - Sn ί ί R R

in which each of the symbols R is identical or different alkyl groups having 1 to 10 carbon atoms, Y is an oxygen or sulfur atom and X is a halogen atom, an acetate group or an acrylate or methacrylate group, 0.02 to 15.0 parts by weight % of a quaternary ammonium salt with surfactant activity.

0.1 to 55% by weight of a mixture of the ammonium salts of a plurality of polyphosphoric acids obtained by neutralizing an aqueous 80 to 86% by weight phosphorus pentoxide solution with ammonia or a basic derivative thereof in a manner which ensures that substantially any hydrolysis of the is suppressed existing phosphoric acid types,

From 0.05 to 30% by weight of a carbamic acid derivative having at least 2 amino groups in the molecule and from 0.02 to 3.0% by weight of one or more hydrotropic substances selected from a representative of the phosphate esters of the formula

R (GHR ₁ OHO)

O Il

(OH).

consist,

wherein R _{1 represents} a hydrogen atom or a methyl group, η has an average value of about 5.0 to 9.0, R represents the same or different branched or straight-chain alkyl groups or alkyl-substituted aromatic hydrocarbon groups having 8 to 15 carbon atoms, χ is 1 or 2 and χ + y is 3 and the molar ratio of the compounds where χ is 1 to those in which χ is 2 is equal to about 1.3: 1 to 10.0: 1, or from the alkali metal or ammonium salts of a xylenesulfonic acid and at least 55 wt .-% water (DE-OS 2650579).

The quaternary ammonium compounds used in this agent are used because of their pronounced surface-active properties. The disadvantage is that the biocidal properties and washing out resistance of these compounds in the wood body are relatively low and come only at high concentrations in the manner required for a wood preservative effect.

Object of the invention

The aim of the invention is a wood preservative in dispersion form based on water-soluble ammonium compounds and water-insoluble active ingredients with improved wood preservative action and higher washing resistance from the wood body.

Explanation of the essence of the invention

The problem to be solved is to increase the wood-protecting effect of water-soluble ammonium compounds in a mixture together with water-insoluble active ingredients.

This object is achieved by a wood preservative with water-soluble active ingredients based on ammonium compounds of the general formula

- Έ - Rr

R _{1 is} a hydrocarbon radical having up to 20 carbon atoms, R ₂ and R _{3 are} any alkyl and / or aryl radicals having up to 8 carbon atoms,

R _{4 is} an alkyl radical having up to 5 carbon atoms or a hydrogen radical, X "is the anion of an organic or inorganic acid and water-insoluble hydrogens based on known biocidal organotin compounds and / or based on known biocidal halogenated organic compounds and these active ingredients in the wood preservative Dispersion, dissolved, according to the invention, the wood preservative as the active substance 65 to 89.2Gew .-% of a compound

R

N -

R ₃

0.05 to 10% by weight of active compounds based on organotin compounds and / or halogenated organic compounds, 0.1 to 10% by weight of the reaction product of a mono- to polychlorinated hydrocarbon having up to 20 carbon atoms with a dialkylamine and 0.1 to 15% by weight .-% of a compound of the general formula

2+

Ή - Ra -IT II -3 Jl-

wherein R _{5 is} any, also branched hydrocarbon radical having up to 20 carbon atoms, which is optionally also chloro-substituted and optionally ring-like instead of R _{4 is} linked to one of the two nitrogen atoms, XY " ² the radicals mono- or polybasic organic or inorganic Acids and are the same or different, and this component in a ratio of 0.1 to 4 to the weight ratio of the active ingredient based on organotin compounds and / or in a ratio of 0.1 to 8 to the weight ratio of the active ingredient based on the halogenated organic compounds optionally, the active ingredients are dispersed in water using 0.1 to 5% by weight of a nonionic surfactant, or dissolved in an organic solvent, and the dispersion optionally contains 0.1 to 2% by weight of a corrosion inhibiting agent.

Advantageously, the radical R _{5 is} a hydrocarbon radical having 7 to 20 carbon atoms. As low has been found that the amine-based agent to 92 wt .-% of the compound

- CH.

CH ₃ COO

and at 8 wt .- $

from the connection

CH-

H -

CH,

U-H I

2 +

CH ₃ COO

consists.

As organotin compounds with advantage bis-tri-n-butyltin oxide, tri-n-butyl-tin acetate, tri-n-butyl-tin-phosphate, tri-n-butyl-tin chloride used singly or in a mixture and as halogenated ^ Organic compounds pentachlorophenol, dichlorodiphenyltrichloromethylmethane y-hexachlorocyclohexane used singly or in a mixture.

It is also advantageous to formulate the wood preservative so that the water-soluble active ingredients in water, and the water-insoluble active ingredients are dissolved in diesel oil and the latter is dispersed in the aqueous solution.

In cases where a particularly high wash-out resistance is required, it has proved expedient to disperse the water-dissolved active ingredients in a solution of the water-insoluble active ingredients in diesel oil.

The wood preservative according to the invention has a better wood-protecting effect than known agents. A higher leaching resistance from the wood body is achieved by an improved binding of the individual components, especially the diamine component, to the cellulose framework of the wood. By combining the water-soluble and water-insoluble components synergistic effects are achieved. Another advantage is that the new wood preservative highly toxic chlorinated compounds are replaced by less harmful compound.

embodiments Example 1:

The following solutions are used to prepare a wood preservative: In a stirred vessel, 42.5 kg of dimethyl dodecylammonium acetate are initially mixed together.

prepared by reacting dodecyl alcohol with dimethylamine at 360 ^° C. over an aluminum oxide catalyst and reacting the resulting tertiary amine with acetic acid,

7.0 kg of 1,11 tetramethylundecyldiammonium diacetate prepared by reacting undecane 1,11-dibromide with dimethylamine and then reacting the diamine with acetic acid, 0.5 kg of dimethyldodecylamine, 0.85 kg of disodium hydrogen phosphate, 50 kg of water.

In a further stirred vessel, 20 kg of dichlorodiphenyltrichloromethane and 5.0 kg of y-hexachlorocyclohexane are dissolved in 75 kg of a diesel oil fraction and then 5 kg of oxethylate of fatty alcohols (nonionic) are added.

Thereafter, 4 kg of the solution based on diesel oil and 96 kg of the aqueous solution are dispersed. The wood preservative is applied flat on the wood to be protected. A preventive protection is achieved against the infestation of blue mushrooms, wood-destroying mushrooms and insects by the application of approx. 14g active substance per square meter wood. To determine the effectiveness in comparison to the wood preservatives mentioned in the prior art (DE-AS 1 299 405) serial dilutions of the stock solutions containing 50% by weight of active compound were prepared and the efficacy against blue fungi (Pullularia pullulans) was tested therewith. For this purpose, in each case 100 g of solution per square meter of wood were applied to test specimens made of pine wood and exposed to the attack of a pure culture of wood-discoloring blue-fungal fungi. The limiting concentration of active substance in the solution, at which there was still a visible inhibition of the formation of blueness on the wood surface or exposed inner wood parts, was determined. For the test pieces impregnated with the wood preservative of the invention, a limiting concentration of efficacy lower by a factor of 2.1 than that impregnated with a wood preservative according to the prior art was obtained. In order to determine the washing-out resistance of the substances, test specimens which had been soaked in the dilution series were exposed to 35 hours of water storage prior to the action of the blue fungi. For the test specimens without water storage, the efficacy limit concentration is lower than for specimens previously subjected to water storage. The ratio of the limit concentrations of both test series is a measure of the different washout resistance of the wood preservatives. The smaller this ratio is and the closer it approaches 1, the better is the washout resistance of the wood preservative. For the wood preservative according to the invention a ratio of 2.3 was determined, while for a prepared according to the prior art means this value is 3.2.

Example 2:

To prepare a wood preservative, the following solutions are used: First, mixed together in a stirred vessel:

49.0 kg of the reaction product of a Octadecanfraktion with chlorine at 50 ⁰ C, from which the unreacted paraffin was separated (41.1%) and the reaction of the resulting Ocetadecanylchlorids (49%) and the higher chlorinated Octadecans (9.9%) with Dimethylamine and subsequent reaction of the amine mixture with acetic acid, 1.0 kg dimethyldecylamine, 0.5 kg disodium hydrogen phosphate, 50.0 kg of water.

In a further stirred vessel, 15 kg of bis-tri-n-butyltin oxide are dissolved in 85 kg of a diesel oil fraction and 5 kg of oxethylate of nonylphenol (nonionic) are added.

Subsequently, 5 kg of the solution based on diesel oil are distributed in 95 kg of the aqueous solution.

The wood preservative is applied in a quantity of 15g / m ² on the wood to be protected.

Preventive protection against the infestation of blue mushrooms, wood-destroying fungi and insects is achieved. The ratio of wash-out resistances is 2.8. An efficacy limit concentration was found to be 1.9 times lower than that of a known wood preservative.

Example 3:

10 kg of the aqueous solution according to Example 2 and 90 kg of the active ingredients dissolved in diesel oil according to Example 1 are mixed with one another in a mixing vessel and, for this purpose, a further 300 kg of diesel oil fraction are added.

The resulting wood preservative is used in an amount of 16g / m ² and protects as a preventive measure against blue fungus, wood-destroying fungi and insects.

The ratio of wash-out resistances is 2.5. The determined limit concentration of the effectiveness is lower by a factor of 1.8 than with known wood preservatives.

Claims (3)

Invention claim: 1. Wood preservative with water-soluble active ingredients based on ammonium compounds of the general formula % " ^l i - ^R 2
R ^ Ri is a hydrocarbon radical having up to 20 carbon atoms, R ₂ and R _{3 are} any alkyl and / or aryl radicals having up to 8 carbon atoms, R _{4 is} an alkyl radical having up to 5 carbon atoms or a hydrogen radical, X "the anion of an organic or inorganic acid and water-insoluble active ingredients based on known biocidal organotin compounds and / or based on known biocidal halogenated organic compounds and these active ingredients in the wood preservative Dispersion are present, characterized in that the wood preservative as the active substance 65 to 89.2Gew .-% of a compound 0.05 to 10% by weight of active compounds based on organotin compounds and / or halogenated organic compounds, 0.1 to 10% by weight of the reaction product of a mono- to polychlorinated hydrocarbon having up to 20 carbon atoms with a dialkylamine and 0.1 to 15% by weight .-% of a compound of the general formula  ΕΤΙ 2 + tf 2 contains, where R _{5 is} any, also branched hydrocarbon radical having up to 20 carbon atoms, which is optionally also chloro-substituted and optionally ring-like instead of R _{4 is} linked to one of the two nitrogen atoms, XY ^2- the radicals mono- or polybasic organic or inorganic acids and the same or different and this component in a ratio of 0.1 to 4 to the weight ratio of the active ingredient based on organotin compounds and / or in a ratio of 0.1 to 8 to the weight ratio of the active ingredient based on the halogenated organic compounds and the active ingredients optionally using 0.1 to 5% by weight of a nonionic surfactant are dispersed in water or dissolved or dispersed in an organic solvent and the dispersion optionally contains 0.1 to 2% by weight of a corrosion inhibiting agent. 2. Wood preservative according to item 1, characterized in that the radical R _{5 is} a hydrocarbon radical having 7 to 20 carbon atoms. Wood preservative according to item 1, characterized in that the amine-based active agent is 92% by weight of the compound IT - CH- CH ₃ COO and 8% by weight of the compound CH ₇ H - IJ - CH ₇ ! ³ N-H 2 +