SK20352000A3 - Agents and method for the protective treatment of wood - Google Patents

Abstract

The invention relates to agents for the protective treatment of wood against decay and insect infestation, which contain at least the following ingredients: a) between 10 and 90 parts coaltar oil, b) between 2 and 20 parts of a quaternary ammonium compound with biocide action, and c) between 10 and 90 parts water. The agents provided for by the invention are easily prepared stable emulsions characterized, among other things, by good penetrating power, significantly reduced odour of the treated wood, absence of undesirable coaltar concentrations on the surface, markedly reduced bleeding of the treated wood during summer temperatures, significantly greater effectiveness despite a lower coaltar oil content and lower toxicity than pure coaltar oil.

Description

Wood preservative

Technical field

The present invention relates to a coal tar oil composition for the protective treatment of wood. It further relates to a method for the protective treatment of wood using the compositions according to the invention.

BACKGROUND OF THE INVENTION

The use of coal tar oil to protect wood against rot and insect attack has been known since the mid-19th century and has been used to ensure the durability of poles, fences, sleepers, etc. Previously, the use of coal tar oil in the form of emulsions in water or aqueous protective salt solutions (zinc salts, copper) has been tried. However, this form of use did not produce the desired results, so that tar oil was mostly used undiluted. Attempts have also been made to improve the unsatisfactory stability of coal tar oil emulsions by "homogenization (in a manner similar to that of milk) or by treatment with specially adapted dispersing devices (e.g. ULTRATURRAX®) and various additives (AT-patent specification 86925, EP-A-0227430 ). These processes have high equipment costs and are energy intensive. Recently, interest in the application of coal tar oil emulsions in water has increased again, in particular in this way to partially eliminate or lessen the disadvantages of non-inherited coal tar oil, such as unpleasant odor, tendency to sweat and sticky-treated wood surface. -5,098,472).

A disadvantage of this known process is that the emulsions are relatively unstable.

A further disadvantage is that the effective proportion of the coal tar pitch in the emulsion is reduced by the proportion of water and emulsifier (s), so that the amount introduced needs to be increased to provide effective and lasting protection.

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Therefore, it was an object of the present invention to overcome or alleviate the disadvantages of the known processes for the production and use of tar oil emulsions.

SUMMARY OF THE INVENTION

This object is achieved according to the invention by means according to claim 1 and by a treatment method according to claim 6.

Surprisingly, it has been found that stable emulsions and microemulsions of coal tar tar oil in water can be produced by simple mixing without special equipment costs by using biocidally active quaternary ammonium compounds, optionally by using polar solvents such as glycol derivatives. The biocidal effect of the quaternary ammonium compounds not only compensates for the dilution of tar oil, it also appears - and this could not be expected - that the penetration depth and spectrum of activity is clearly above those of pure undiluted tar oil.

The compositions of the invention comprise at least the following components:

a) 5-90 parts, preferably 10-90 parts, of coal tar oil,

b) 2-20 parts of biocidally active quaternary ammonium compounds,

c) 10-90 parts water.

All amounts are referred to herein as parts by weight.

Suitable biocidally active quaternary ammonium compounds are, for example:

N-C 6-20 -alkyl-N, N-dimethyl-N-benzylammonium chloride, -bromide or iodide *)

N, N-di-C6-20-alkyl-N, N-dimethylammonium chloride, -bromide or-iodide *)

NC ₆ -2o-alkyl salts *) of pyridine, quinoline etc.

N-C6-20-N, N, N-trimethylammonium chloride, -bromide or iodide *)

N, N-di-C6-20-alkyl-N-methyl-N-poly (oxethyl) ammonium salts *) • · ·· • ·

*) Salts of other inorganic acids or organic carboxylic acids, e.g. acetate, propionate, sulfate, etc.

For example, it was found that an emulsion containing only 30% tar oil, about 10% cationic active ammonium compound, about 5% adjuvants and 55% water was at least twice effective against wood-destroying fungi compared to unintegrated pure coal tar oils.

By using these means, it is possible to utilize the excellent and long-term experience based on the efficiency of coal tar oil while significantly reducing shortcomings such as odor, sweating at high ambient temperatures, elutability and oily, sticky wood surface.

At the same time, better, i.e. more even and deeper distribution of the preservative in the wood is achieved, and - this seems to be particularly advantageous - the wood may be more wet than when using pure tar oil. As a result, it is possible to significantly reduce the drying time and energy in drying the raw wood, e.g. sleepers and masts.

A further advantage of the compositions according to the invention is that, unlike pure tar oil, these compositions can be processed at normal ambient temperature. Indeed, pure tar oil can only be processed at 100 ° C, which is dependent on its viscosity and flowability, and this is associated with high energy consumption. In contrast to these properties of tar oil, there are also properties such as deep penetration and optimal distribution in wood.

The distinctive odor of coal tar oil is mainly due to two tricyclic aromatics, e.g. naphthaline and alkylnaphthaline. These can only be partially removed by distillation, since after their complete removal tar oil with too high a viscosity is formed, at which viscosity is not yet acceptable at 100-120 ° C. The compositions according to the invention make it possible, in their preparation, to use tar oils of higher viscosity and thus strongly odorous. This facilitates or even allows the use of coal tar oil even in sensitive environments, e.g. sleepers for the subway.

The compositions according to the invention preferably contain up to 20 parts of a polyglycol compound for improving storage stability. These include, for example, polyethylene glycols and polypropylene glycols, as well as their alkyl and aryl ethers and esters. Particularly preferred are polyethylene glycol compounds such as polyethylene glycol, ethoxylated phenols and diethylene glycol monobutyl ether.

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

resins, binders, polymers, waxes dyes pigments antioxidants odor control markers (Tracer)

The compositions preferably comprise one or more components from the group of resins, binders, waxes, dyes and pigments.

Particularly preferred binders are alkyd resins and similar resins based on natural oils, such as linseed oil or soybean oil, in particular those which are water-soluble or water-dilutable by reaction with ethylene oxide or propylene oxide.

To extend the spectrum of activity, the compositions of the invention preferably additionally contain an effective amount of one or more insecticides, fungicides, algicides or bactericides.

For example, one or more of the following active ingredients may be included:

amphotensides with biocidal activity methylbenzimidazol-2-ylcarbamate

1,2-benzisothiazolone-3 biguanide with biocidal effect of organic and inorganic boron compound α-tert-butyl-α- (p-chlorophenethyl) -1H-1,2,4-triazole-1-ethanol 2-sec-butylphenyl- (±) - cis-4- [3-tert-Butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine N-methylcarbamate 5-chloro-2-methyl-4-isothiazolin-3-one

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

1- (6-chloro-3-pyridinyl) -methyl-4,5-dihydro-N-nitro-1H-imidazol-2-amine chlorohexidine and its chlorinated phenols salts, e.g. tetra- and pentachlorophenol chloronitrobenzene derivatives

1- [4- (2-chloro-a, a, a-trifluoro-p-tolyloxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea

1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea α- [2- (4-chlorophenyl) ethyl] - α- (1,1-dimethylethyl) -1H-1,2,4-triazole -1-ethanol cyano (4-fluoro-3-phenoxyphenyl) methyl 3- (2,2-dichloroethyl-2,2-dimethylcyclopropanecarboxylate (RS) - α-cyano-3-phenoxybenzyl (RS) -2- ( 4-chlorophenyl) -3-methylbutyrate α-cyano-3-phenoxybenzylisopropyl-2,4-chlorophenylacetate N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxylic acid amide di (guanidinoctyl) amine

3- (2,2-Dibromovinyl-2,2-dimethyl) - α- (cyano-m-phenoxybenzyl-1R, 3R) -cyclopropanecarboxylate

- [2- (2,4-Dichlorophenyl) -1,3-dioxalan-2-ylmethyl] -1H-1,2,4-triazole

1- [2- (2,4-Dichlorophenyl) -4-propyl-1,3-dioxalan-2-ylmethyl] -1H-1,2,4-triazole

(+) - 3- (2,2-Dichloro-vinyl-2,2-dimethyl) -cyclopropane-1-carboxylic acid 3-phenoxybenzyl ester 3- (2,2-Dichloro-vinyl-2,2-) - dimethyl) cyclopropane-1-carboxylic acid

O, O-diethyl-O- (a-kyanbenzylidénamino) thiophosphate

0,0-diethyl-0-3,5,6-trichloro-2-pyridyltiofosfát

0,0-dietylditiofosforyl-6-chlórbenzoxazolón

5,6-dihydro-2-methyl-1,4-oxathiine-3-carboxylic acid anilide

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) metylditiofosfát 3 _I, 5-dimethyl-tetrahydro-1,3,5-tiadiazíntion- (2) salts dimetylalkylmínu dithiocarbamates, metal and amine salts of ethyl 2- (4-phenoxy) ethylcarbamate

2- (2-furanyl) -1H-benzimidazole haloacetic acid as well as amides and esters thereof

6,7,8,9,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,3,4-benzodioxothiepien-3-hexachlorocyclohexane

8-hydroxyquinoline and its halogenated derivatives of 2-iodobenzoic acid anilide

3-Iodo-3-propynyl butylcarbamate copper-8-oxyquinoline

N-methyl-1-naphthylcarbamate

2-methyl-4-isothiazolin-3-one methylenebistiocyanate nitroalkanols with biocidal action

N-nitroso-N-cyclohexylhydroxylamine and its salts

N-nitroso-N-phenylhydroxylamine and its salts norbomendimethane-hexachlorocyclosulfite ··

2-N-octyl-4-isothiazolin-3-one tin organo compounds, for example tin tributyloxide and tin tributyl benzoate phenylphenols

2-isopropoxyphenyl N-methylcarbamate

N-propyl-N- [2- (2,4-trichloro-6 _I) ethyl] imidazole-1-carboxamide pyridine-2-thiol-1-oxide and salts thereof as well as salicylanilide haloigenované derivatives of (4-ethoxyphenyl) [ 3- (4-fluoro-3-phenoxyphenyl) propyl] (dimethyl) silane

N- (1,1'-N-tetrachloroethylthio) -Se-1'-tetrahydrophthalimide tetrachloroisophthalic acid dinitrile

2- (thiazol-4-yl) benzimidazole

2-tiokyanometyltiobenzotiazol

- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-ol

- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan-2-one

N-trichloromethylthio-S.e.'.-tetrahydrophthalimide N-trichloromethylthiophthalimide

N-tridecyl-2,6-dimethylmorpholine

By adding binders such as e.g. drying alkyd resins, acrylates or other polymers, the treated wood surfaces can be mechanically and optically improved, coupled with a further reduction in the mobility (washing and leaching) of coal tar oil. In addition, the systems according to the invention can be modified with dyes or pigments in comparison with the coal tar oil alone so that the treated wood can be dyed. By adding waxes, it is possible to achieve a matt surface of the treated wood, which is associated with a strong water repellency which reduces the water uptake dropwise without compromising the moisture exchange through the vapor phase.

For example, the formulations of the invention are manufactured as follows:

(I) 5-90 parts of coal tar oil, e.g. WEI type C, optionally mixed with ·· ·· at slightly elevated temperature (approx. 50 ° C)

(II) 2-20 parts a cationically active surfactant, e.g. N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate, and stirred until homogeneous, then added (III) 0-20 parts a glycol derivative, e.g. diethylene glycol monobutyl ether, and stirred until homogeneous, then added (IV) 0-20 parts a stabilizer / solubilizer, e.g. p-nonylphenol ethoxylate (EO = 10-14), and again stirred until homogeneous and all cooled. After cooling, it is added (IN) 10-90 parts water and mixed until a homogeneous emulsion is formed.

In this preparation, stable, milky (opaque) or clear low viscosity mixtures are formed which can be introduced into the wood without good temperature in the pressure boiler (using vacuum and pressure) with good penetration. Depending on the ratio of the components I, II and V, an added amount of 20-80 kg / m ^{3 of} wood is required for extensive wood protection.

The use of the compositions according to the invention is preferably carried out in a vacuum pressure boiler by introducing the compositions into the wood to be protected by different pressures. Process steps include a pre-vacuum phase, a flood phase while maintaining vacuum, and a pressure phase. Alternatively, the process is terminated with a final vacuum. The amount of preservative introduced is checked by weighing. With the easily impregnable wood or wood type, the water content of the compositions can be further increased compared to the examples.

Preferably, the impregnation is carried out without heating, i.e. at about ambient temperature. If necessary, the water introduced into the wood together with the compositions can be removed by heating. If the compositions additionally contain polymers which are suitable for curing due to the elevated temperature, the wood may be treated with hot steam. This steam treatment leads to a subsequent diffusion of the steam. ·· and more even distribution of resources, together with more efficient fixation. The polyethylene glycols optionally containing the compositions provide a dimensionally stabilizing effect. Wood treated with these compositions has a significantly lower tendency to crack.

Overall, the compositions according to the invention have the following advantages over coal tar oil:

1. High emulsion stability.

2. Possible use at normal ambient temperature.

3. Good protective agent distribution also for medium damp wood.

4. Significantly reduced odor of treated wood.

5. No disturbing accumulation of tar oil on treated wood.

6. Strongly suppressed 'leakage' of treated wood at summer temperatures.

7. Preservation of surface structure and veining visibility.

8. Low surface color.

9. Compatibility with usual varnishes and glazes.

10. Significant increase in effect through lower content of coal tar oil in preparations.

11. Possibility of coloring treated wood.

12. Low leachability of treated wood, thus no relevant local environmental pollution.

13. Lower toxicity compared to pure coal tar oil.

14. Reduced crack formation when drying treated wood.

15. Possibility of using highly deodorized tar oils with high viscosity.

DETAILED DESCRIPTION OF THE INVENTION

The following examples illustrate the composition and efficacy of the compositions of the invention and the implementation of the process of the invention.

Comparative Example 1 (not according to the invention) · · podľa nie nie nie nie príklad príklad príklad príklad príklad príklad príklad príklad príklad príklad nie · · · · · · · · · · · · · · · · ·

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

Comparative Example 2 (not according to the invention)

50 parts coal tar oil 10dielov an anionically active emulsifier 40 parts waters

Example 1

40 parts coal tar oil 8 parts N-cocoalkyl-N, N-dimethyl-N-benzylamóniumacetátu 4 parts 10 parts nonylphenol ethoxylate (8-12 EO groups) of diethylene glycol monobutyl ether 38 parts waters

Example 2

30 parts coal tar oil 10 parts N, N-didecyl-N-methyl-N-poly (ethoxylate) ammonium acetate 4 parts 56 parts nonylphenol ethoxylate (about 14 EO groups) of water

Example 3

50 parts coal tar oil 10 parts N-cocoalkyl-N, N-dimethyl-N-benzyl ammonium chloride 10 parts polyethylene glycol (molecular weight approx. 300) 30 parts waters

parts of coal tar oil

Example 4 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium chloride parts of diethylene glycol monobutyl ether parts of water

The products designated in Examples 1-4 and in Comparative Examples 1-2 were incorporated into the top layer of pine wood at different pressures and tested for biological activity according to DIN EN 113. The results are summarized in Table 1 below.

Table 1

Biological activity against wood-destroying fungi ¹⁾

Example # Tar oil content [%] Relative efficiency ^of> [%] S1 100 100 S2 50 <50 1 40 130 2 30 145 3 50 165 4 30 90

• ¹⁾ The assessment was based on limit values against 4 wood-destroying fungi after aging (EN 73).

²⁾ A coal tar oil was assigned a biological effect of 100%.

It is striking that the formulations according to the invention, which are referred to as Examples 1 to 4, have a markedly enhanced effect due to the addition of cationic compounds despite the lower tar oil content.

It can be seen from Table 1 that the efficiency gains in Examples 1 to 4, based on &lt; RTI ID = 0.0 &gt; 99. &lt; / RTI &gt;

998 9 99

9 99

9999 9999

the actual content of coal tar oil is 1: 3 to 1: 5. Example 5 40 parts coal tar oil 8 parts N-cocoalkyl-N, N-dimethyl-N-benzylamóniumacetátu 4 parts nonylphenol ethoxylate (8-12 EO groups) 10 parts diethylene glycol monobutyl ether 8 parts binder *) 30 parts waters

*) Water-dilutable alkyd resin obtained by cooking fatty acid linseed oil, pentaerythritol and polyethylene glycol (molecular weight approx. 600).

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

*) Pigment paste obtained by spreading transparent red iron oxide into polyethylene glycol (molecular weight approx. 300)

Example 7 parts of coal tar oil parts of N-cocoalkyl-N, N-dimethyl-N-benzylammonium chloride parts of polyethylene glycol (molecular weight approx. 300) parts of wax *) parts of water

*) polyvinyl ether wax warmed previously dissolved in coal tar tar oil •) · · · · · · · · · ·) · · · · · · · · · · · ··· ·· ·· ··· ··

Example 8 parts of coal tar oil parts of N, N-didecyl-N-methyl-N-poly (oxyl) ammonium chloride parts of diethylene glycol monobutyl ether parts of N-methyl-1-naphthylcarbamate (Sevin) *) parts of water

*) Previously dissolved in tar oil

Example 9

A concentrate was prepared according to the following formula:

parts of coal tar oil, type B WEI parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate parts of binder, prepared by heating 94 parts of linseed oil and parts of maleic acid to 180 ° C followed by esterification with 3 parts of polyethylene glycol (10 EO-groups) at 195 ° C.

The concentrate thus obtained was diluted 1: 9 with water to give an emulsion ready for use.

Example 10

A concentrate was prepared according to the following procedure:

parts of coal tar oil type B WEI parts of N, N-didecyl-N-methyl-N-poly (oxyl) ammonium propionate parts of binder, prepared by heating 92 parts of soybean oil and parts of maleic acid to 180 ° C followed by esterification with 5 parts of polypropylene glycol (12 POgroups) at 170 ° C silicone antifoam parts · 99 · 99 99 99 99 99 99 99 99 99 99 99

1 part propiconazole 3 parts waters Example 11 A concentrate was prepared according to the following formula: 70 parts coal tar oil, type B WEI

parts of N, N-didecyl-N-methyl-N-poly (oxyl) ammonium propionate parts of binder prepared by heating 85 parts of polybutadiene oil and 5 parts of maleic acid to 150 ° C followed by esterification with 10 parts of polyethylene glycol (10 EO-groups) at 150 [deg.] C.

% of the colorant dissolved in the oil

The concentrate thus obtained was diluted 1: 9 with water to give an emulsion ready for use.

Example 12

A concentrate was prepared according to the following formula:

parts of coal tar oil, type B WEI parts of N, N-didecyl-N, N-dimethylammonium chloride, 80% in water parts of binder, prepared by heating 80 parts of linseed oil and parts of neopentyl glycol to 170 ° C followed by reaction with 8 parts of ethylene oxide under pressure parts of diethylene glycol monobutyl ether

The concentrate thus obtained was diluted 1: 9 with water to give an emulsion ready for use.

Claims (7)

PATENT CLAIMS A composition for the protection of wood against rot and insect attack, characterized in that it comprises at least the following components: (a) 5-90 parts of coal tar oil b) 2-20 parts of a biocidally active quaternary ammonium compound c) 10-90 parts water, paste consistency is excluded. Composition according to claim 1, characterized in that it additionally contains up to 20 parts of a polyethylene glycol compound for improving stability. Composition according to claim 1 or 2, characterized in that it additionally contains resins, binders, waxes, dyes and / or pigments. Composition according to one of Claims 1 to 3, characterized in that it contains at least one alkyd resin or a similar resin based on natural oils such as linseed or soybean oil as a binder. Composition according to one of Claims 1 to 4, characterized in that it contains additionally effective proportions of biocides, such as insecticides, fungicides, algicides or bactericides, for widening the spectrum of action. A method of protective wood treatment, characterized in that the wood is impregnated with a composition according to one or more of claims 1 to 5 using pressure differences. Method according to claim 6, characterized in that it is impregnated without heating.