CZ299917B6 - Composition for protective treatment of wood - Google Patents

Abstract

In the present invention, there is disclosed a composition for the protective treatment of wood against rot and attack by insects, comprising at least the following components: a) 5 to 90 parts by weight of coal-tar oil; b) 2 to 20 parts by weight of a biocidally active quaternary ammonium compound being selected from the group consisting of inorganic or organic carboxylic acid salts of N,N-di-Ci6-20-alkyl-N-methyl-N-poly(oxoethyl)ammonium, N,N-di-Ci6-20-alkyl-N,N-dimethylammonium, N-Ci6-20-alkylpyridinium and N-Ci6-20-alkylquinolinium; and N-Ci8-20-alkyl-N,N-dimethyl-N-benzylammonium acetate; and c) 10 to 90 parts by weight of water.

Description

Wood preservative

Technical field

The present invention relates to a coal tar tar oil composition for protective wood treatment. 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 pylons, fences, sleepers, etc. The use of coal tar oil in the form of emulsions in water or aqueous protective salt was soon tested. solutions (salts of zinc, copper). 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 the coal tar oil emulsions by "homogenization" (in a manner similar to that used for milk) or by treatment with specially adapted dispersing devices (eg UETRA-TURRAX) and various additives (patent application).

2, AT 86925. EP 0227430). These processes have high equipment costs and are energy intensive. In the new era, interest in the application of coal tar oil emulsions in water has increased again. in particular because the disadvantages of undiluted coal tar oil, such as an unpleasant odor, tendency to swell and the sticky surface of the treated wood are partially eliminated or reduced in this way (US 5,098,472).

The disadvantage of this known progresses it. that the emulsions are relatively unstable. Another drawback is that. This means that the effective proportion of coal tar in the emulsion is reduced by the proportion of water and emulsifier (s), so that it is necessary to increase the amount introduced to ensure effective and lasting protection.

The LJ around the present invention was therefore to eliminate or alleviate the disadvantages of the known processes for the production and use of tar oil emulsions.

SUMMARY OF THE INVENTION In accordance with the invention, the present invention is accomplished by means of the compositions of claim 1 and the method of treatment of claim 6.

Surprisingly, it has been found that the use of biocidally active quaternary ammonium compounds, or the use of polar solvents such as glycol derivatives, with simple mixing without special equipment costs can produce stable emulsions and microemulsions of coal tar oil in water. The biocidal effect of the quaternary ammonium compounds not only compensates for the dilution of the tar oil, it also appears - and this could not be expected that the depth of penetration and the 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 to 90 parts. preferably 10 to 90 parts, of coal tar oil;

b) 2 to 20 parts of biocidally active quaternary ammonium compounds;

c) 10 to 90 parts water.

All amounts are referred to herein as parts by weight.

Suitable biocidally active quaternary ammonium compounds are, for example:

- I 0/7 299917 Bo

NC _with 2'-alkyl-N, N'-dimethyl-N-benzylanioniumeloronide, -bromide or iodide of Ν, Ν-Cf,-alkyl-N, N-dimethylammonium chloride-bromide or -iodide.

N-CV ₂ oalkyl salts * ^{1 of} pyridine, quinoline etc.

NC _{6 2 ((} alkyl-NN, N trimethylammonium chloride-bromide or NN-di-Cfc <) -alkyl-N-methyl-1'-N-poly (oxethyl) ammonium salts ⁺¹ ) Salts of other halides may also be salts of other inorganic acids or organic carboxylic acids such as acetate, propionate, sulfate, etc.

io

For example, it was found that an emulsion containing only 30% tar oil, ca. 10% cationic active ammonium compound, ca. 5% of adjuvants and 55% of water have proven to be at least twice as effective against wood decaying fungi compared to undiluted pure coal tar oil.

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

At the same time, a 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. This can significantly reduce drying time and energy when drying raw wood. eg 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. Against these tar oil properties are properties such as deep penetration and optimum distribution in wood.

The distinctive odor of coal tar oil is in particular a process of two- and three-alkali aromatics, for example 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 still not acceptable at 100 to 120 ° C. The compositions according to the invention make it possible to use tar oils of a higher viscosity and thus strongly odorous. This makes it easier or even possible to use coal tar oil in sensitive environments such as metro sleepers.

The compositions of 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 agents, Tracer o

C7. 299917 B6

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

Particularly preferred binders are alkyd resins and the like natural oil based resins such as linseed oil or soybean oil. especially those which are water-soluble by reaction with ethylene oxide or propylene oxide. or. water-dilutable.

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

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

Biocidal amphotensides methylbenzimidazol-2-ylcarbamate 1.2 Benzisothiazolone-3 biguanide with biocidal effect of organic and inorganic boron compound (α-tert-bulyl-α-β-chlorophenethyl) -! H 1,2,4-triazole-1-ethanol

2 sec-butylphenyl 1-N-methylcarbamate (± E-cis-4- [3-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine 5-chloro-2-methyl-4-isolhiazoline- 3-on

2- (4-chlorophenyl) -3-cyclopropyl-1H-1,2,4-triazol-1-yl) bulan 2-ol (6-chloro-3-pyridinyl) methyl-4,5-dihydro N-nitro-11I- Imidazol-2-amine from? chlorhexidine and its salts chlorinated phenols, eg tetra- and pent-chlorophenol chlorobenzene derivatives - [4- (2-chloro-oxo-trifluoro-p -tolyloxy) -2-fluorophenyl] -3 (2,6-difluorobenzoyl) urea 1- (4- chlorophenyl) -3- ((2,6-difluorobenzoyl) urea) - [2- (4-chlorophenyl) ethyl] <x- <1,1-dimethylethyl) -1H 1,2,4-triazole-1-ethanol cyano (4-fluoro- 3-phenoxyphenyl) methyl 1-3- (2,2-dichloro-1-2,2-dimethylcyclopropanecarboxylate (RS) -α-cyano 3-phenoxybenzyl- (RS) -2 (4-chlorophenyl) -3-methylbutyrate α-cyano-3-phenoxy benzyl isopropyl-2,4-chlorophenylacetate N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxylic acid di- (guanidinoctyl) amine

3- (2,2-Difluoromethyl-2,2-dimethylmethyl) - C - (cyano- m -phenoxy benzyl-1R, 3R) cyclopropane carboxylic acid 1- (2- (2,4-dichlorophenyl) - 1,3-dioxolane-2-> 1-Imethyl] -1H-1,2,4-triazolo- (2- (2,4-dichlorophenyl) 4-propyl-1,3-dioxolan-2-ylmethyl) -1H-1,2 (+) - 3- (2,2-Dichloro-vinyl-2,2-dimethyl) -cyclopropane-1-carboxylic acid 3-phenoxy-benzyl ester and 3- (2,2-di-chloro-vinyl) -2,2-dimethyl-cyano-3,3-phenoxy-benzyl ester 4-triazole cyclopropane-1-carboxylic acid

O, O-diethyl-O-3,5,6-trichloro-2-pyridylthiophosphate

O.O-Diethyldithiophosphoryl-6-chlorobenzoxazolone

5.6-Dihydro-2-methyl-1,4-oxathizine-3-carboxanilide N, N dimethyl-N-phenyl (N'-fluoromethylthio) sulfamide

N, ^N'-dimelhvl -tolyl- (Ν 'fluoromethylthio) -sulfamide

O, O-dimethyl-S (2-methylamino-2-oxoethyl) dithiophosphate with O, O-dimethyl-S4N-phthalimidoylmethyldithiophosphate

3,5-Dimethyl tetrahydro-1,3,5-thiadiazinethione (2) dimethylalkylamine salts dithiocarbamates. metal and amine salts ethyl 2- (4-phenoxyphenoxy) ethylcarbaniate

Bó (2-fluorine I) - 1 H bnn / imidazide of haloenoic acid as well as their amides and esters

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

8-hydroxyquinoline and its halogenated derivatives 2-iodo-benzoic acid anilide 3-iodo-3-propynyl-butylcarbamate copper-8-oxyquinoline N-methyl-1-naphthylcarbamate io 2-methyl M-isothiazolin-3-one methyl N-nitroso-N-cyclohexylated nitroalkanols nitroalkanols Ihydroxy lamin and its salts N-nitroso-N-phenylhydroxy lamin and its salts i? norbomendimethane hexachlorocyclosulfite 2-N-octyl M-isothiazole-3-one organosin tin compounds, eg tin loxide tributions and tin benzoate tributyl phenylphenols

2-isopropoxyphenyl-N-methylcarbamal

N-propyl-N- [2- (4,6-trichlorophenoxy) ethyl-imidazole-1-carboxamide pyridin-2-thiol-1-oxide and its salts salyl anilide and its halogenated derivatives of (4-ethoxyphenyl) [3- (4-fluoro-3-phenoxyphenyl) propyl] (dimethyl) silane N- (1,1,2,2-tetrachloroethylthio) 3,6,7,8-tetrahydro phthalimide

2? tetrahloroisophthalic acid, disodium 1

2- (thiazol-M-yl) benzimidazo-2-thiocyanomethylthiobenzothiazole

- (1,2,4-triazol-1-yl) -1- (4-chlorophenoxy) -3,3-dimethylbutan 2-ol 1 (1,2,4 tria / ol 1-yl) I (4-chloro-oxy) 3.3-thiomethylbulan-2 -he

N-trichloromethylthio-3,6,7,8-tetrahydrophthalimide N-trichloromethylthiophthalimide N-lridecyl-2,6-methylmorpholine

By adding binders such as drying alkyd resins, acrylates or other polymers, the surfaces of the treated wood can be mechanically and optically improved, which is associated with a further reduction in the mobility (washing and leaching) of the coal tar oil. In addition, the systems according to the invention can be treated with dyes or pigments in such a way that dyeing of the treated wood can be effected against the tar tar oil alone. By adding waxes, it is possible to achieve a matt surface of the treated wood, which is associated with a strong water repellency, which also decreases the water intake dropwise without disturbing the moisture exchange through the vapor phase.

For example, the compositions of the invention are prepared as follows:

(I) 5 to 90 parts of coal tar oil, e.g. WEI type C., optionally mixed with (II) 2 to 20 parts of a cationic active surfactant such as N, N- at moderately elevated temperature (ca. 50 ° C) didecyl-Nm ethyl N-poly (oxethyl) ammonium propionate, and mixed until homogeneous, then added (111) 0 to 20 parts of a glycol derivative, e.g., diethylene glycol monobutyl ether, and stirred until homogeneous, then added ( IV) 0 to 20 parts of a stabilizer / solubility agent, e.g., p-nonylphenol ethoxylal (1 () - 10 to 14), and blended again until homogeneous and cooled completely. After cooling, add

- 4 C_7. 299917 B6 (V) 10 to 90 parts water and mixed until a homogeneous emulsion is formed.

In this preparation, stable, milky (opaque) or clear mixtures of low viscosity are formed which can be incorporated into the wood without any increase in temperature by pressure in the boiler (using vacuum and pressure) with good penetration. Depending on the ratio of the components of Formulation II and V, an amount of 20 to 80 kg / m &lt; 3 &gt; of wood is required for extensive wood protection.

The use of the composition according to the invention is preferably carried out in a vacuum pressure boiler so. by incorporating the means into the wood to be protected by means of pressure differences. The process steps include a pre-vacuum phase. the flood phase while maintaining the vacuum, and the pressure phase. The process is optionally terminated with a final vacuum. The amount of preservative introduced is checked by weighing.

For easily impregnable wood. or. 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, 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 subsequent diffusion and more even distribution of the compositions, along with more efficient fixation. The ivet hylenglycols that are optionally included in the formulations provide these formulations with a dimensionally stabilizing effect. Wood treated with these agents has a significantly lower tendency to crack,

Overall, the compositions of the invention have the following advantages over camouflage tar oil:

1. high emulsion stability,

2. Possible use at normal ambient temperature.

w 3. good distribution of the preservative also for medium damp wood,

4. significantly reduced odor of treated wood,

5. no disturbance to the accumulation of tar oil and treated wood;

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

7. preservation of surface structure visibility and granulation.

8. Small surface color.

9. compatibility with conventional lacquers and glazes,

10. a marked increase in effect despite the lower content of coal tar oil in the 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 cracking during drying of treated wood,

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

DETAILED DESCRIPTION OF THE INVENTION

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

Comparative Example 1 (not according to the invention)

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

- 5 Q ~ L 299917 Bo

Comparative Example 2 (not according to the invention) of coal tar oil parts of anionic emulsifier? 40 parts water

Example 1 parts of coal tar oil and about 8 parts of N-cocoalkyl-N, N-dimethyl-1-N-benzylammonium acetate parts of one of the phenoxyethoxy (8-12 EO-groups) parts of diethylene glycol monobutyl ether parts of water?

Example 2 30 parts 10 parts 4 parts

56 parts of coal tar tar oil

N, N-didecyl-N-ethyl-N-poly (oxyl) ammonium acetate nonylphenol ethoxylate (ca 14 EO-groups) water

Example 3 parts of coal tar oil parts of N-cocosalkyl-N, N-dimethyl-N-benzylammonium chloride parts of polyethylene glycol (wet weight ca. 300) parts of water io Example 4 parts of coal tar oil of parts N, N-didecyl-N-methyl-N - poly (oxyl) ammonium chloride parts of diethylene glycol monobutyl ether parts of water

The products designated in Examples 1 to 4 and Comparative Examples 1 to 2 were incorporated into the top layer of pine wood using a pressure difference and the biological activity was tested according to DIN EN 113. The results are summarized in Table 1 below.

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Table 1

Biological activity against wood decaying fungi ¹ '

Fixklod c. CibSáh tar oil [%] ___1 ~ 4-4 4 LC1UU-L V Jll efficiency ² ) [%] Sl 100 ALIGN! 100 ALIGN! S2 50 <50 1 40 1 30 2 30 145 3 50 165 4 30 90

the bases for evaluation were the limit values against 4 wood decaying fungi after aging (EN 73) and a biological effect equal to 100% was assigned to ¹ coal tar oil

It is striking. The compositions according to the invention, which are exemplified in Examples 1 to 4, have a markedly increased effect due to the lower tar oil content due to the addition of cationic compounds.

Table 1 shows that the efficiency gains of Examples 1 to 4, based on the actual coal tar oil content, are 1: 3 to 1: 5.

Example 5 parts 8 parts 4 parts 10 parts 8 parts 30 parts coal tar oil

N-Cocosalkyl-N, N-Dimethyl-N-Benzylaniomumacelalion I Phenolate Boxes (8-12 EO-Groups) of Diethylene Glycohonobutyl Lether Binder ¹ Water ¹ Water-dilutable alkyd resin obtained by cooking flaxseed fatty acid with pentaerythritol and to polyethylene glycol (molecular weight ca. 600).

Example 6 parts of coal tar oil parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium lactal parts of nonylphenol ethoxyl (about 14 EO-groups) parts of iron oxide paste * 20% parts of water

- 7 GB ¹ 299 917 B6 pigment paste obtained by grinding transparent red iron oxide in polyethylene glycol (mol. Weight ea. 300)

Example 7

50 parts 10 parts and i0 parts 2 parts coal tar oil N-cocosalkyl-N, N-dimethyl-N-benzylammonium chloride polyethylene glycol (molecular weight ca. 300) wax * ' 28 díl water

´ poles of guilt lether wax warm previously dissolved in coal tar oil j

Example 8

30 parts 20 5 parts 20 díl 1 part coal tar oil N, N didecyl-N-methyl-N-poly (octyl) ammonium chloride diethylene glycol monobutyl ether N-methyl-1-naphthylcarbamate (Sevin) * ' 44 parts water

previously dissolved in tar oil

Example 9

A concentrate was prepared according to the following formula

60 parts 20 parts 20 parts coal tar oil, type B WE1 N.N didecyl-N-methyl-N-poly (oxethyl) ammonium propionate Binder prepared by heating 94 parts of linseed oil and 3 parts of maleic acid to 35 180 ° C followed by esterification with 3 parts of polyethylene glycol (10 EO groups) at 195 ° C

The concentrate thus obtained was diluted with water at a ratio of 1.9 to give an emulsion ready for use

Example 10

A concentrate was prepared according to the following formula;

65 parts 15 díl 4? 15 parts coal tar oil, type B WE1 N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate binder, prepared by heating 92 parts of soybean oil and 3 parts of maleic acid to 180 ° C and then esterifying with 5 parts of polypropylene glycol (12 PO groups) at 170 ° C 1 part 1 parts 5 (even 3 parts s i 1 i final power foams propiconazole water

Example 1 1

A concentrate was prepared according to the following formula:

parts of coal tar oil, type B WE1

Ν, Ν-didcyl-N-methyl-N-pula (oxyl) dihydroxide) binder prepared by heating 85 parts of polybutadiene oil and 5 parts of malic acid to 15 ° C followed by esterification with 10 parts of polyethylene glycol (10 EO-groups) at 150 ° C a portion of the oil soluble dye

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

Example 12

21)

A concentrate was prepared according to the following formula:

parts of coal tar oil, type B WE1 part of Ν, did-didecyl-N, N-dimethylammonium chloride, 80% in water parts of binder, prepared by heating 80 parts of linseed oil and 12 parts of neopentyl glycol to 170 ° C and subsequent reaction with 8 parts of ethylene oxide 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 1. A composition for the protection of wood against rot and insect attack, comprising at least the following components: (a) 5 to 90 parts by weight of coal tar oil: B) 2 to 20 parts by weight of a biocidal active quaternary ammonium compound selected from the group consisting of an inorganic acid salt or an organic carboxylic acid NN-diC1,220-alkyl-N-methyl N-poly (oxethyl) atmmonium, N, N-di -C ₆ 7-alkyl-1, N, N-dimethylammonium. NC <, 2o-alkylpyridinium and NC ₍ > 20-alkylquinolinium and N C 20 -alkyl-N N -dimethyl-N-benzylammonium acetate): (c) 10 to 90 parts by weight of water. 2. A composition according to claim 1, further comprising up to 20 parts of the polyethylene glycol compound to improve stability. 45 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 as a binder. 50 such as linseed oil or soybean oil. -9EN 299917 36 Composition according to one of Claims 1 to 4, characterized in that: The composition of claim 1, characterized in that it contains additionally effective proportions of biocides, such as insecticides, fungicides, algicides or bactericides, for widening the spectrum of action. 6. A method of protective treatment of wood, characterized in that: The process according to claim 1, wherein the wood is impregnated with a composition according to one or more of claims 1 to 5 when pressurized in the boiler. 7. The method of claim 6, wherein the process is impregnated without heating.