HUP0102995A2 - Agents and method for the protective treatment of wood - Google Patents

Abstract

The subject of the invention is a preparation based on coal tar oil, suitable for the protective treatment of wood. Another subject of the invention is a method for wood preservative treatment using the composition according to the invention. The product is characterized by containing at least the following components: a) 5-90 parts coal tar oil b) 2-20 parts quaternary ammonium compound with biocidal effect c) 10-90 parts water. HE

Description

PUBLICATION .·> .: .”···/

EXAMPLE^, _{method and process for} wood preservative treatment

The invention relates to a coal tar oil-based composition suitable for the protective treatment of wood. The invention also relates to a method for the protective treatment of wood using the composition according to the invention.

It has been known since the mid-19th century that coal tar oil can be used to protect wood from rot and insects, and coal tar oil is still used to make electricity poles, fences and thresholds more durable. Early experiments were made to use coal tar oil in the form of an emulsion prepared with water or an aqueous solution of protective salts (zinc, copper salts), but this form of application did not produce the desired results, so tar oils were mostly used undiluted. The insufficient stability of the coal tar oil emulsion was also attempted to be increased by “homogenization” (analogous to the process used for milk) or by treatment in a dispersing device specially developed for this purpose (e.g. ULTRA-TURRAX®) or by various additives (AT-PS 86 925, EP-A 0 227 430). These processes not only require expensive machinery but also consume a lot of energy. Recently, the use of coal tar oil as an aqueous emulsion has come into the spotlight again, not least because it can eliminate or at least reduce some of the disadvantages of undiluted coal tar oil, such as its unpleasant odor, tendency to sweat, and the sticky surface of the treated wood (US-A-5

098 472).

The disadvantage of the known method is that the emulsion is relatively unstable and that the effective proportion of coal tar oil is reduced by the proportion of water and emulsifier, so that more must be used to achieve effective and long-lasting protection.

The aim of the present invention was to eliminate or reduce the known disadvantages of the production and application of tar oil emulsions.

The above object is achieved by the compositions according to claim 1 and the method according to claim 6.

Surprisingly, we have found that stable aqueous emulsions and microemulsions can be prepared from coal tar oil by simple mixing and without special equipment using biocidal quaternary ammonium compounds and optionally a polar solvent, such as a glycol derivative. The biocidal effect of the quaternary ammonium compounds not only compensates for the dilution of the tar oil, but - and this was not foreseen - the composition penetrates deeper into the wood than pure, undiluted tar oil; its spectrum of action is broader than that of amazé.

They contain at least the following ingredients according to the invention:

a) 5-90 parts, preferably 10-90 parts, of coal tar oil b) 2-20 parts of a biocidal quaternary ammonium compound

c) 10-90 parts water.

Here and below, parts are parts by mass.

Biocidal quaternary ammonium compounds include:

N-C8-C20-alkyl-N,N-dimethyl-N-benzyl ammonium chloride, bromide or iodide N,N-di-C6-C20-alkyl-N,N-dimethyl ammonium chloride, bromide or iodide, pyridine, quinoline, etc. N-C6-C20-alkyl salts,

N-C6-C20-alkyl-N,N,N-trimethylammonium chloride, bromide or iodide

N,N-di-C6-C20-alkyl-N-methyl-N-poly(oxethyl)ammonium salts.

Instead of halides, salts formed with other inorganic acids or organic carboxylic acids are also suitable, for example acetate, propionate, sulfate, etc.

For example, we have found that an emulsion containing only 30% tar oil, about 10% cationic ammonium compound, about 5% excipient and 55% water is at least twice as effective against wood-destroying fungi as undiluted, pure coal tar oil.

With the help of the compositions according to the invention, we can utilize the excellent, long-proven effect of coal tar oil by reducing the disadvantages of odor, sweating in case of higher ambient temperatures, washability and oily, sticky wood surfaces.

In addition, the preservative is better distributed, i.e. more evenly, in the wood, it penetrates deeper, and - this seems particularly significant - the moisture content of the wood can be higher than is permitted when using pure tar oil. Less time and energy are spent on drying raw wood, such as sleepers and electricity poles.

A further advantage of the compositions according to the invention is that the compositions can be processed at normal ambient temperatures, unlike pure tar oil; the processing of pure tar oil, due to its viscosity and flow behavior, takes place at temperatures around 100 °C, and is therefore energy-intensive. The viscosity and density of tar oil also hinder deep penetration and optimal distribution.

The penetrating odor of coal tar oil is mainly caused by two- and three-ring aromatic compounds, such as naphthalene and alkylnaphthalenes. These compounds are only partially removed by distillation, since after their complete removal the viscosity of the tar oil cannot be handled even at 100-120 °C. In the compositions according to the invention, higher viscosity, i.e. highly deodorized tar oil can also be used; this makes it possible to use coal tar oil in some sensitive areas (e.g. the treatment of subway sleepers).

The compositions according to the invention preferably further contain up to 20 parts of a polyglycol compound to increase their (storage) stability. These include, for example, polyethylene glycols and polypropylene glycols and their alkyl and aryl esters.

Particularly preferred are polyethylene glycol compounds, such as polyethylene glycol, ethoxylated phenols and diethylene glycol monobutyl ether.

In addition to the ingredients already mentioned, the compositions according to the invention may also contain, for example, the following substances:

resins, binders, polymers, waxes, dyes, pigments, antioxidants, odor-enhancing tracers.

The compositions preferably contain a resin, a binder, a wax, a dye and/or a pigment.

The binder is particularly preferably an alkyd resin or similar resin based on natural oils such as linseed or soybean oil, most preferably resins which have been reacted with ethylene oxide or propylene oxide to form a water-soluble, water-dilutable resin.

In order to broaden the spectrum of action, the compositions according to the invention preferably further contain one or more insecticidal, fungicidal, algicidal or bactericidal substances in an effective amount.

Among the active ingredients listed below, the compositions according to the invention may contain, for example, one or more active ingredients: biocidal amphoteric surfactants, methyl benzimidazol-2-ylcarbamate, 1,2-benzisothiazol-3-one, biocidal biguanides, inorganic and organic boron compounds, α-tert-butyl-α(p-chlorophenethyl)-1H-1,2,4-triazole-1-ethanol,

2-sec-butylphenyl-N-methylcarbamate, (±)-cis-4-[3-(tert-butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine,

-chloro-2-methyl-4-isothiazolin-3-one,

2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,

-(6-chloro-3-pyridinyl)-methyl-4,5-dihydro-N-nitro-1H-imidazol-2-amine, chlorhexidine and its salts, chlorinated phenols, such as tetra- and pentachlorophenol, 1-[4-(2-chloro-a,c,a-trifluoro-p-tolyloxy)-2-fluorophenyl]-3-(2,6-difluorobenzoyl)urea,

-(4-chlorophenyl)-3-(2,6-difluorobenzoyl)urea, a-[2-(4-fluoro-3-phenoxyphenyl)methyl-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate, (RS)-a-cyano-3-phenyloxybenzyl-(RS)-2-(4-chlorophenyl)-3-methylbutyrate, a-cyano-3-phenoxybenzylisopropyl-2,4-chlorophenylacetate,

N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxylic acid amide, di-(guanidino-octyl)amine,

3-(2,2-dibromovinyl-2,2-dimethyl)-a-(cyano-m-phenoxybenzyl-1R,3R)-cyclopropanecarboxylate,

-[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-1H,1,2,4-triazole,

-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1Η, 1,2,4-triazole, (+)-3-(2,2-dichlorovinyl-2,2-dimethyl)cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester,

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

O,O-diethyl-O-(α-cyanobenzylideneamino)thiophosphate,

O, O-diethyl-O-3,5,6-trichloro-2-pyridyl-thionophosphate,

O,O-diethyldithiophosphoryl-6-chlorobenzoxazolone,

5,6-dihydro-2-methyl-1,4-oxathine-3-carboxanilide,

N,N-dimethyl-N’-phenyl-(N-fluoromethylthio)sulfamide,

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

O,O-dimethyl-S-(2-methylamino.2.oxoethyl)-dithiophosphate,

O,O-dimethyl-S-(N-phthalimido)methyldithiophosphate, ,5-dimethyltetrahydro-1,3,5-thiadiazinethi-2-one, dimethylalkylamine salts, dithiocarbamates, metal and amine salts, ethyl 2-(4-phenoxyphenoxy)ethylcarbamate,

2-(2-furyl)-1H-benzimidazole, haloacetic acids, their amides and esters,

6,7,8,9,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methane-2,3,4-benzodioxo-thiepene-3-oxide, hexachlorocyclohexane,

8-hydroquinoline and its halogenated derivatives,

2-iodobenzoic acid anilide,

-iodo-3-propynylbutylcarbamate, copper-8-oxyquinoline,

N-methyl-1-naphthylcarbamate,

2-methyl-4-isothiazolin-3-one, methylene bisthiocyanate, biocidal nitroalkanols,

N-nitroso-N-cyclohexylhydroxylamine and its salts,

N-nitroso-N-phenylhydroxylamine and its salts, norbornene dimethanohexachlorocyclosulfite, 2-N-octyl-4-isothiazolin-3-one, organotin compounds such as tributyltin oxide, tributyltin benzoate, phenylphenols, 2-isopropoxyphenyl-N-methylcarbamate,

N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide, pyridine-2-thiol-1-oxide and its salts, salicylanilide and its halogenated derivatives, (4-ethoxyphenyl)-[3-(4-fluoro-3-phenoxyphenyl)propyl]-(dimethyl)silane, N-(1,1,2,2-tetrachloroethylthio)-3,6,7,8-tetrahydrophthalimide, tetrachloroisophthalic acid dinitrile, 2-(thiazol-4-yl)benzimidazole, 2-thiocyanomethylthiobenzothiazole,

-(1,2,4-triazol-1-yl)-1 -(4-chlorophenoxy)-3,3 -dimethylbutan-2-ol, 1 _(i ,2,4-triazol-1-yl)-1 -(4-chlorophenoxy)-3,3-dimethylbutan-2-one, N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide, N-trichloromethylthiophthalimide, N-tridecyl-2,6-dimethylmorpholine.

Binders, such as drying alkyd resins, acrylates or other polymers, can improve the surface of the treated wood mechanically and optically, and the mobility (washing out, sweating) of the coal tar oil is further reduced. The systems according to the invention - in contrast to coal tar oil - can be modified in such a way that the treated wood can be colored by adding only dyes or pigments. By adding wax, the treated wood can be provided with a matt surface, while at the same time a strong water-repellent effect is created, which greatly reduces the absorption of water droplets without hindering the exchange of gas-phase moisture.

The compositions according to the invention can be prepared, for example, by adding (I) 5-90 parts of coal tar oil (e.g. WEI C type) optionally at a slightly elevated temperature (about 50 °C) (II) 2-20 parts of a cationic surfactant, e.g. N,N-didecyl-N-methyl-N-poly(oxethyl)ammonium propionate and homogenizing the mixture by stirring, then (III) 0-20 parts of a glycol derivative, e.g. diethylene glycol monobutyl ether, and homogenizing the mixture by stirring, then (IV) 0-20 parts of a stabilizer/dissolution mediator, e.g. p-nonylphenyl ethoxylate (EO = 10-14), stirring the mixture again until homogeneous, and then cooling. Then (V) 10-90 parts of water are added and the mixture is stirred until it becomes a homogeneous emulsion.

The above operations produce stable, milky (opaque) or clear, low-viscosity mixtures that penetrate well into the wood without raising the temperature, using a boiler pressure process (using vacuum and pressure). Depending on the proportion of components L, II. and V., the amount required for comprehensive protection of the wood is 2080 kg/m ³ of wood.

The compositions according to the invention are preferably used in vacuum/boiler pressure equipment, whereby the composition is introduced into the wood to be protected by means of pressure differences. The steps of the process are a preliminary vacuum phase, an immersion phase while maintaining the vacuum, and a pressure phase. The amount of the composition introduced into the wood is determined by weighing on a scale. In the case of easily impregnable wood species, the water content of the composition can be increased even further compared to that given in the examples.

Preferably, the impregnation is carried out without the application of heat, i.e. at approx. ambient temperature. If necessary, the water introduced into the wood together with the preparation can be removed by heat treatment. If the preparation additionally contains a polymer that cures at a higher temperature, the wood can be treated with hot steam. This steam treatment leads to subsequent diffusion and a more uniform distribution of the agent, and its fixation is also more effective. The polyethylene glycol optionally present in the preparation imparts a dimensionally stable effect to the grains, and the wood treated with it is significantly less prone to cracking.

In summary, the compositions of the invention have the following advantages compared to coal tar oil:

1. Emulsions are very stable.

2. Emulsions can be applied at ambient temperature.

3. The preservative is well distributed even in wood with a medium moisture content.

4. The smell of treated wood is greatly reduced.

5. There are no tar oil deposits on the treated wood.

6. In summer temperatures, treated wood “bleeds” much less.

7. The pattern and structure of the wooden surface remain visible.

8. Surface discoloration is slight.

9. The product is compatible with standard varnishes and treatment materials.

10. Although the preparations contain less coal tar oil, their effect is definitely stronger.

11. Treated wood can be stained.

12. Treated wood is less susceptible to leaching, so it does not burden the environment.

13. It has lower toxicity compared to pure coal tar oil.

14. Treated wood will develop fewer cracks when dried.

15. Highly deodorized, high-viscosity tar oil can also be used in the preparations.

The following examples illustrate in more detail the composition and effect of the compositions according to the invention, as well as the process according to the invention.

Comparative Example 1 (not according to the invention)

100 parts coal tar oil, undiluted, application at 110 °C

Comparative Example 2 (not according to the invention) part coal tar oil part anionic emulsifier part water.

Example 1 part coal tar oil part N-coco alkyl-N,N-dimethyl-N-benzyl ammonium acetate part nonylphenol ethoxylate (8-12 EO groups) part diethylene glycol monobutyl ether part water.

Example 2: part coal tar oil part N,N-didecyl-N-methyl-N-poly(oxethyl)ammonium lactate part nonylphenol ethoxylate (about 14 EO groups) part water.

Example 3 part coal tar oil part N-coco alkyl-N,N-dimethyl-N-benzyl ammonium chloride part polyethylene glycol (molecular weight approx. 300)

Example 4: Part coal tar oil Part N,N-didecyl-N-methyl-N-poly(oxethyl)ammonium chloride Part diethylene glycol monobutyl ether Part water.

Black pine wood was impregnated with the products of Examples 1-4 and Comparative Examples 1 and 2 using differential pressure and the biological effect was tested using a method developed on the basis of DIN EN 113. The results are summarized in Table 1 below.

Table 1

Biological effect against wood-destroying fungi ¹ )

Example number Tar oil content [%] relative effect ² ) [%] total 1 100 100 total 2 50 <50 1 40 130 2 30 145 3 50 165 4 30 90

^υ The evaluation was based on a limit value against 4 wood-destroying fungi after aging (EN 73) ²⁾ The biological effect of coal tar oil was taken as 100%.

It appears that the compositions according to Examples 1-4, i.e. according to the invention, despite their lower tar oil content, are more effective due to the cationic compounds.

As can be seen from Table 1, the ratio of the amplification of the effect - in relation to the specific amount of coal tar oil - is between 1:3 and 1:5.

Example 5 part coal tar oil part N-coco alkyl-N,N-dimethyl-N-benzyl ammonium acetate part nonylphenol ethoxylate (8-12 EO groups) part diethylene glycol monobutyl ether part binder*) part water ^} water-dilutable alkyd resin obtained by boiling linoleic fatty acid, pentaerythritol and polyethylene glycol (molecular weight approx. 600)

Example 6 part coal tar oil part N,N-didecyl-N-methyl-N-poly(oxyethyl)ammonium lactate part nonylphenol ethoxylate (approx. 14 EO groups) part iron oxide paste*) 20% part water

*) pigment paste obtained by grinding transparent iron oxide red in polyethylene glycol (molecular weight approx. 300)

Example 7 part coal tar oil part N-coco alkyl-N,N-dimethyl-N-benzyl ammonium chloride part polyethylene glycol (molecular weight approx. 300) part wax*) part water ^; polyvinyl ether wax dissolved in warm coal tar oil

Example 8 part coal tar oil

* 5 parts N,N-didecyl-N-methyl-N-poly(oxyethyl)ammonium chloride - 20 episodes diethylene glycol monobutyl ether Part 1 N-methyl-1-naphthylcarbamate*) 44 episodes water

^} dissolved in coal tar oil

Example 9

We produce concentrate according to the following recipe:

60 episodes B WEI type coal tar oil 20 episodes N,N-didecyl-N-methyl-N-poly(oxyethyl)ammonium propionate 20 episodes binder, prepared by heating a mixture of 94 parts linseed oil and 3 parts maleic acid to 180 °C and then esterifying it with 3 parts polyethylene glycol (10 EO groups) at 195 °C

The resulting concentrate is diluted with water in a ratio of 1:9 to obtain a ready-to-use emulsion.

Example 10

We produce concentrate according to the following recipe:

65 episodes B WEI type coal tar oil 15 episodes N,N-didecyl-N-methyl-N-poly(oxethyl)ammonium propionate 15 episodes binder, prepared by heating a mixture of 92 parts soybean oil and 3 parts maleic acid to 180 °C, followed by esterification with 5 parts polyethylene glycol (12 EO groups) at 170 °C Part 1 silicone defoamer Part 1 propiconazole 3 parts water.

Example 11

We produce concentrate according to the following recipe:

part B WEI type coal tar oil part N,N-didecyl-N-methyl-N-poly(oxyethyl)ammonium propionate part binder, prepared by heating a mixture of 85 parts polybutadiene oil and 5 parts maleic acid to 150 °C and then esterifying it with 10 parts polyethylene glycol (10 EO groups) at 150 °C, part oil-soluble dye.

The resulting concentrate is diluted with water in a ratio of 1:9 to obtain a ready-to-use emulsion.

Example 12

We produce concentrate according to the following recipe:

part B WEI type coal tar oil part N,N-didecyl-N,N-dimethylammonium chloride (80 %, in water) part binder, prepared by heating a mixture of 80 parts linseed oil and 12 parts neopentyl glycol to 170 °C and then reacting with 8 parts ethylene oxide under pressure part diethylene glycol monobutyl ether

The resulting concentrate is diluted with water in a ratio of 1:9 to obtain a ready-to-use emulsion.

Claims (7)

Patent claims 1. A preparation for the protective treatment of wood against rot and insect attack, characterized in that it contains at least the following ingredients: a) 5-90 parts coal tar oil b) 2-20 parts of a biocidal quaternary ammonium compound c) 10-90 parts water. 2. A composition according to claim 1, characterized in that it additionally contains up to 20 parts of a polyethylene glycol compound to improve stability. 3. The composition according to claim 1 or 2, characterized in that it additionally contains a resin, a binder, a wax, a dye and/or a pigment. 4. A composition according to any one of claims 1-3, characterized in that it contains as a binder at least one alkyd resin or a similar resin based on natural oil, such as linseed oil or soybean oil. 5. The composition according to any one of claims 1-4, characterized in that it additionally contains an effective amount of a biocidal, such as an insecticidal, fungicidal, algicidal or bactericidal substance, to expand the spectrum of action. 6. A method for protecting wood, characterized in that the wood is impregnated with the composition according to any one of claims 1-5 by applying pressure differences. 7. The method according to claim 6, characterized in that the impregnation is carried out without applying heat. Game - oS · 6.