AU4356699A - 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

1 Compositions and process for the protective treatment of wood The present invention relates to compositions based on coal-tar oil for the protective treatment of 5 wood. It furthermore relates to a process for the protective treatment of wood' using the compositions according to the invention. The use of coal-tar oil for protecting wood against rot and attack by insects has been known since 10 the middle of the 19th century and is still customarily employed for preserving poles, fences, sleepers etc. Even early on, attempts were made to use coal-tar oil in the form of emulsions in water or aqueous protective salt solutions (zinc salts, copper salts). However, 15 these use forms did not give the desired results, and most tar oils were still used undiluted. In addition, attempts were made to improve' the unsatisfactory stability of coal-tar oil emulsions by "homogenization" (analogously to the process used for milk) or by 20 treatment with specifically adapted dispersing apparatus (for example ULTRA-TURRAX@) and diverse additives (AT-PS-86 925, EP-A-0 227 430). These processes involve expensive equipment and consume a lot of energy. More recently, the application of coal-tar 25 oil emulsions in water attracted renewed interest, in particular since in this manner it is possible to partially eliminate or reduce some disadvantages of the undiluted coal-tar oil, such as, for example, the unpleasant odour, the tendency to sweat and the sticky 30 surface of the treated woods (US-A-5 098 472). This known process has the disadvantage that the emulsions are relatively unstable and that, owing to the emulsion, the effective proportion of coal-tar is reduced by the proportion of water and the 35 emulsifier (s) , so that the amount that is applied has to be increased to ensure effective and long-lasting RA4 protection. Accordingly, it was an object of the present invention to eliminate or reduce the disadvantages of 2 the known preparation processes and applications of tar oil emulsions. According to the invention, this object is achieved by the compositions according to claim 1 and 5 the treatment process according to claim 6. Surprisingly, it has been found that, by using biocidally active quaternary ammonium compounds, if appropriate together with polar solvents, such as, for example, glycol derivatives, it is possible to prepare 10 stable emulsions and microemulsions of coal-tar oil in water by simple stirring without any special equipment requirements. Not only doe4 the biocidal action of the quaternary ammonium compounds compensate for the fact that the tar oil is diluted, but it has additionally 15 been found - contrary to expectations - that the depth of penetration and the activity spectrum considerably exceeds those of the pure undiluted tar oil. The compositions according to the invention comprise at least the following components: 20 a) 5-90 parts, preferably 10-90 parts, of coal tar oil b) 2-20 parts of a biocidally active quaternary ammonium compound c) 10-90 parts of water. 25 Here and below, all amounts are stated in parts by mass. Suitable biocidally active quaternary ammonium compounds are, for example: - N-C 8 -2-alkyl-N, N-dimethyl-N-benzylammonium 30 chloride, bromide or iodide*) - N,N-di-C6-20-alkyl-N,N-dimethylammonium chloride, bromide or iodide*) / - N-C 6

-

2 0 -alkyl salts*) of pyridine, quinoline, etc. - N-C 6

-

2 0 -alkyl-N,N,N-trimethylammonium chloride, 35 bromide or iodide*) - N, N-di-C 6

-

2 0 -alkyl-N-methyl-N-poly (ethoxy) ammonium salts * *) Instead ,of the halides, it is also possible for the salts of other inorganic acids or organic carboxylic 3 acids to be present, for example acetate, propionate, sulfate, etc. It has been found, for example, that an emulsion comprising only 30% of tar oil, about 10% of a 5 cationic ammonium compound, about 5% of auxiliaries and 55% of water was at least twice as effective against wood-destroying fungi as undiluted pure coal-tar oil. With the aid of these compositions, it is possible to utilize the excellent activity of coal-tar 10 oil, supported by long-term experience, and at the same time to reduce considerably the disadvantages of odour, of sweating at high ambient temperatures, of elutability and of the oily sticky surface of the wood. Simultaneously, better, i.e. more uniform and 15 deeper, distribution of the protective composition in the wood is achieved and - this appears to be particularly advantageous - the wood can have a higher moisture content than would be possible if pure tar oil was used. Thus, the time and energy for drying the raw 20 wood, for example sleepers and poles, can be reduced considerably. A further advantage of the compositions according to the invention consists in the fact that they can be processed at, normal ambient temperatures, 25 in contrast to pure tar oil. That is to say that pure tar oil, owing to its viscosity and flow behaviour, can only be processed at temperatures of about 100 0 C, which is associated with a high energy input. Moreover, this property of tar oil stands in the way of deep 30 penetration and optimum distribution in the wood. The intense odour of coal-tar oil is caused, in particular, by bi- and tricyclic aromatic compounds, for example naphthalene and alkylnaphthalenes. Only some of these can be removed by distillation since, if 35 they are removed completely, a tar oil is formed which has a viscosity which is too high and not even manageable at 100-120 0 C. Because of the way in which they are prepared, the compositions according to the * invention permit the use even of tar oils of relatively 14C1 4 high viscosity which, accordingly, are highly deodorized, which facilitates the use of coal-tar oil even in sensitive areas, for example sleepers for underground railways, or makes this use possible in the 5 first place. Preferably, the compositions according to the invention additionally comprise up to 20 parts of a polyglycol compound to improve (storage) stability. These include, for example, polyethylene glycols and 10 polypropylene glycols, and their alkyl and aryl ethers and esters. Particular preference is given to polyethylene glycol compounds such as, for example, polyethylene glycol, to ethoxylated phenols and to diethylene glycol 15 monobutyl ethers. In addition to the formulation components already mentioned, the compositions according to the invention may comprise, for example, the following substances: 20 - resins, binders, polymers - waxes - dyes - pigments - antioxidants 25 - odour-masking substances - markers (tracers) They preferably comprise one or more components from the group of the resins, binders, waxes, dyes and pigments. 30 Particularly preferred binders are alkyd resins and similar resins based on natural oils, such as linseed oil or soya oil, in particular those which are water-soluble or water-dilutable owing to reaction with ethylene oxide or propylene oxide. 35 To widen the activity spectrum, the compositions according to the invention preferably STJI ( additionally comprise an effective amount of one or more insecticides, fungicides, algicides or * bactericides.

5 They may comprise, for example, one or more of the following active compounds: Amphoteric surfactants having biocidal action Methyl benzimidazol-2-ylcarbamate 5 1,2-Benzisothiazol-3-one Biguanides having biocidal action Organic and inorganic boron compounds a-tert-Butyl-a- (p-chlorophenethyl) -lH-1, 2, 4-triazol-1 ethanol 10 2-sec-Butylphenyl N-methylcarbamate (±) -cis-4- [3- (tert-Butylphenyl) -2-methylpropyll -2,6 dimethylmorpholine 5-Chloro-2-methyl-4-isothiazolin-3-one 2- (4-Chlorophenyl) -3-cyclopropyl-l- (1H-1, 2, 4-triazol-1 15 yl)butan-2-ol 1- (6-Chloro-3-pyridinyl)methyl- 4 , 5-dihydro-N-nitro-lH imidazol-2-amine Chlorohexidine and its salts Chlorinated phenols, for example tetra- and penta 20 chlorophenol Chloronitrobenzene derivatives 1-[4-(2-Chloro-a,c(,a-trifluoro-p-tolyloxy)-2-fluoro phenyl]-3-(2,6-difluorobenzoyl)urea 1-(4-Chlorophenyl)-3-(2,6-difluorobenzoyl)urea 25 a- [2- (4-Chlorophenyl) ethyl] -a- (1, 1-dimethylethyl) -lH 1,2,4-triazol-1-ethanol Cyano(4-fluoro-3-phenoxyphenyl)methyl 3- (2,2-dichloro ethenyl)-2,2-dimethylcyclopropanecarboxylate (RS) -a-Cyano-3-phenoxybenzyl- (RS) -2- (4-chlorophenyl) -3 30 methylbutyrate ax-Cyano-3-phenoxybenzyl isopropyl-2, 4-dichlorophenyl acetate N-Cyclohexyl-N-methoxy- 2 , 5-dimethylfuran-3-carboxamide Di(guanidinooctyl)amine 35 3- (2, 2-Dibromovinyl-2, 2-dimethyl) -a- (cyano-m-phenoxy benzyl-lR,3R)cyclopropanecarboxylate '5T/ 1-[2- (2,4-Dichlorophenyl) -1,3-dioxolan-2-ylmethyl]-1H- 6 1-[2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl methyl]-lH-1,2,4-triazole 3-Phenoxybenzyl (+)-3-(2,2-dichlorovinyl-2,2-dimethyl) cyclopropane-1-carboxylate 5 c-Cyano-3,3-phenoxybenzyl 3-(2,2-dichlorovinyl-2,2 dimethyl)cyclopropane-l-carboxylate O,O-Diethyl-O-(a-cyanobenzylideneamino) thiophosphate O,O-Diethyl-O-3,5,6-trichloro-2-pyridyl thionophosphate 0,0-Diethyldithiophosphoryl-6-chlorobenzoxazolone 10 5,6-Dihydro-2-methyl-1,4-oxathiine-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) dithio phosphate 15 O,O-Dimethyl-S-(N-phthalimido)methyl dithiophosphate 3,5-Dimethyltetrahydro-1,3,5-thiadiazin-2-thione Dimethylalkylamine salts Dithiocarbamates, metal and amine salts Ethyl 2-(4-phenoxyphenoxy)ethylcarbamate 20 2-(2-Furanyl)-lH-benzimidazole Halogenated acetic acids and their amides and esters 6,7,8,9,10-Hexachloro-1,5,5a,6,9,9a-hexahydro-6,9 methano-2,3,4-benzodioxothiepine 3-oxide Hexachlorocyclohexane 25 8-Hydroxyquinoline and its halogenated derivatives 2-Iodobenzanilide 3-Iodo-3-propinyl butylcarbamate Copper 8-oxyquinoline 1-Naphthyl N-methylcarbamate 30 2-Methyl-4-isothiazolin-3-one Methylene bisthiocyanate Nitroalkanols having biocidal action N-Nitroso-N-cyclohexylhydroxylamine and its salts N-Nitroso-N-phenylhydroxylamine and its salts 35 Norbornene dimethanohexachlorocyclosulfite 2-N-Octyl-4-isothiazolin-3-one 5TR Organotin compounds, for example tributyltin oxide and tributyltin benzoate * Phenylphenols 7 2-Isopropoxyphenyl N-methylcarbamate N-Propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole 1-carboxamide Pyridine-2-thiol 1-oxide and its salts 5 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-tetrahydro phthalimide 10 Tetrachloroisophthalonitrile 2-(Thiazol-4-yl)benzimidazole 2-Thiocyanomethylthiobenzothiazole 1-(1,2,4-Triazol-1-yl)-1-(4-chlorophenoxy)-3,3 dimethylbutan-2-ol 15 1-(1,2,4-Triazol-1-yl)-l-(4-chlorophenoxy)- 3 ,3 dimethylbutan-2-one N-Trichloromethylthio-3, 6, 7, 8-tetrahydrophthalimide N-Trichloromethylthiophthalimide N-Tridecyl-2, 6-dimethylmorpholine 20 By addition of binders such as, for example, drying alkyd resins, acrylates or other polymers, it is possible to improve the surfaces of the treated woods mechanically and optically, and at the same time to reduce the mobility (leaching and bleeding) of the 25 coal-tar oil even further. The systems according to the invention can furthermore, in contrast to coal-tar oil on its own, be modified by addition of dyes or pigments, such that it is possible to stain the woods treated. By addition of waxes, it is possible to 30 achieve matting of the surfaces of the woods treated, in combination with a strong water-repelling effect which reduces the uptake of liquid water without obstructing moisture exchange via the vapour phase. The preparations according to the invention are 35 prepared, for example, as follows: (I) 5-90 parts of coal-tar oil, for example WEI ST type C, are initially charged and, if appropriate at slightly 8 elevated temperature (about 50 0 C), admixed with (II) 2-20 parts of cationic surfactant, for example N,N-didecyl-N-methyl-N-poly 5 (ethoxy)ammonium propionate, and the mixture is stirred until homogeneity is achieved; (III) 0-20 parts of glycol derivative, for example diethylene glycol monobutyl 10 ether, are then added and the mixture is stirred until homogeneity is achieved, (IV) 0-20 parts of stabilizer/solubilizer, for example p-nonylphenol ethoxylate 15 (EO = 10-14), are then added and the mixture is once more stirred until homogeneity is achieved, and the batch is cooled. After cooling, 20 (V) 10-90 parts of water are added and the mixture is stirred until a homogeneous emulsion has formed. In this preparation process, stable, milky (opaque) or clear low-viscosity mixtures are formed 25 which can be introduced with good penetration into the wood using the boiler pressure method (use of reduced pressure and superatmospheric pressure), without raising the temperature. Depending on the proportion of the formulation components I, II and V, the total 30 amount that has to be introduced for a comprehensive protection of the wood is 20-80 kg/M 3 of wood. The compositions according to the invention are preferably applied in vacuum boiler pressure units such that the compositions are introduced into the wood to 35 be protected using differences in pressure. The process steps include a pre-vacuum phase, a flood phase during which the vacuum is maintained, and a pressure phase. If appropriate, the process is concluded by applying a final vacuum. The amount of the protective composition 9 introduced is controlled by weighing. In the case of woods or wood species which soak easily, it is possible to increase the water content in the compositions even more, compared with the examples. 5 The impregnation is preferably carried out without heat input, i.e. approximately at ambient temperature. If required, the water which is introduced into the wood together with the compositions can be removed 10 by treatment with heat. If the preparations additionally comprise polymers which are curable at elevated temperatures, it is possible to treat the wood with hot steam. This steam treatment then results in a rediffusion and more even distribution of the 15 compositions, combined with a more effective fixing. Polyethylene glycols, which are an optional constituent of the preparations, impart dimension-stabilizing properties to the preparations, combined with a significantly reduced tendency of the wood thus treated 20 to crack. Altogether, the compositions according to the invention have the following advantages compared with coal-tar oil: 1. high stability of the emulsions, 25 2. use at normal ambient temperature is possible, 3. good distribution of the protective composition even in woods with an average moisture content, 4. strongly reduced odour of the woods treated, 5. no annoying tar oil enrichments on the treated 30 wood, 6. strongly reduced "bleeding" of the treated wood at hot temperatures, 7. the surface structure and the grain remain visible, 35 8. only slight discoloration of the surface, 9. compatibility with customary varnishes and R) clearcoats, 10. considerably enhanced activity in spite of a lower * content of coal-tar oil in the preparations, _C1 10 11. option to stain the treated woods, 12. less leaching of the treated woods, and consequently no relevant local environmental stress, 5 13. low toxicity compared with pure coal-tar oil, 14. less cracking when drying the treated wood, 15. option of using strongly deodorized, highly viscous tar oils. The examples below illustrate the composition 10 and the effect of the compositions according to the invention and the practice of the process according to the invention. Comparative Example 1 (not according to the invention) 15 100 parts of coal-tar oil, undiluted use at 110'C Comparative Example 2 (not according to the invention) 50 parts of coal-tar oil 20 10 parts of anionic emulsifier 40 parts of water Example 1 40 parts of coal-tar oil 25 8 parts of N-coco fatty alkyl-N,N-dimethyl-N benzylammonium acetate 4 parts of nonylphenol ethoxylate(8-1 2 EO groups) 10 parts of diethylene glycol monobutyl ether 30 38 parts of water Example 2 30 parts of coal-tar oil 10 parts of N,N-didecyl-N-methyl-N 35 poly (ethoxy) ammonium lactate 4 parts of nonylphenol ethoxylate (about 14 EO T R4 groups) ' 56 parts of water 11 Example 3 50 parts of coal-tar oil 10 parts of N-coco fatty alkyl-N,N-dimethyl-N benzylammonium chloride 5 10 parts of polyethylene glycol (MW about 300) 30 parts of water Example 4 30 parts of coal-tar oil 10 5 parts of N,N-didecyl-N-methyl-N poly (ethoxy) ammonium chloride 20 parts of diethylene glycol monobutyl ether 45 parts of water 15 The products characterized in Examples 1-4 and Comparative Examples 1-2 were applied to pine sapwood using pressure differences, and the biological effect was examined using a process modelled on DIN EN 113. The results are summarized in Table 1 below. 20 Table 1 Biological action against wood-destroying fungi') Example No. Tar oil content Relative activity [%] [%] Cl 100 100 C2 50 <50 1 40 130 2 30 145 3 50 165 4 30 90 Evaluation was based on the limit values against 25 4 wood-destroying fungi after ageing (EN 73) 2) The biological action of coal-tar oil is taken to be 100%. It is evident that the preparations according 3,) to the invention mentioned as Examples 1 to 4 have 12 considerably increased activity owing to the addition of cationic compounds, in spite of the lower tar oil content. As can be seen from Table 1, the activity 5 increase in Examples 1 to 4 is from 1:3 to 1:5, based on the effective coal-tar oil contents. Example 5 40 parts of coal-tar oil 10 8 parts of N-coco fatty alkyl-N,N-dimethyl-N benzylammonium acetate 4 parts of nonylphenol ethoxylate (8-12 EO groups) 10 parts of diethylene glycol monobutyl ether 15 8 parts of binder*) 30 parts of water *) Water-dilutable alkyd resin, obtained by boiling down linoleic acid, pentaerythritol and polyethylene glycol (MW about 600) 20 Example 6 30 parts of coal-tar oil 10 parts of N,N-didecyl-N-methyl-N poly (ethoxy) ammonium lactate 25 4 parts of nonylphenol ethoxylate (about 14 EO groups) 6 parts of iron oxide paste*) 20% 50 parts of water *) Pigment paste, obtained by grinding transparent red 30 iron oxide in polyethylene glycol (MW about 300) Example 7 50 parts of coal-tar oil 10 parts of N-coco fatty alkyl-N,N-dimethyl-N 35 benzylammonium chloride 10 parts of polyethylene glycol (MW about 300) 2 parts of wax*) 28 parts of water 13 *) Polyvinyl ether wax, pre-dissolved in hot coal-tar oil Example 8 5 30 parts of coal-tar oil 5 parts of N,N-didecyl-N-methyl-N poly (ethoxy) ammonium chloride 20 parts of diethylene glycol monobutyl ether 1 part of 1-naphthyl N-methylcarbamate 10 (Sevin)*) 44 parts of water *) Pre-dissolved in tar oil Example 9 15 A concentrate was prepared according to the following recipe: 60 parts of coal-tar oil, type B WEI 20 parts of N,N-didecyl-N-methyl-N poly(ethoxy)ammonium propionate 20 20 parts of binder, prepared by heating 94 parts of linseed oil and 3 parts of maleic acid at 180*C, followed by esterification with 3 parts of polyethylene glycol (10 EO groups) 25 at 195 0 C. The resulting concentrate was diluted with water in the ratio 1:9 to give the ready-to-use emulsion. 30 Example 10 A concentrate was prepared according to the following recipe: 65 parts of coal-tar oil, type B WEI 15 parts of N,N-didecyl-N-methyl-N 35 poly (ethoxy) ammonium propionate 15 parts of binder, prepared by heating 92 parts of soya oil and 3 parts of maleic acid at 1800C, followed by * esterification with 5 parts of 44.' 1 14 polypropylene glycol (12 PO groups) at 1700C 1 part of silicone antifoam 1 part of propiconazole 5 3 parts of water Example 11 A concentrate was prepared according to the following recipe: 10 70 parts of coal-tar oil, type B WEI 10 parts of N,N-didecyl-N-methyl-N poly (ethoxy) ammonium propionate 19 parts of binder, prepared by heating 85 parts of polybutadiene oil and 5 parts of 15 maleic acid at 1500C, followed by esterification with 10 parts of polyethylene glycol (10 EO groups) at 1500C 1 part of oil-soluble dye 20 The resulting concentrate was diluted with water in the ratio 1:9 to give the ready-to-use emulsion. Example 12 25 A concentrate was prepared according to the following recipe: 60 parts of coal-tar oil, type B WEI 10 parts of N,N-didecyl-N,N-dimethylammonium chloride, 80% in water 30 19 parts of binder, prepared by heating 80 parts of linseed oil and 12 parts of neopentyl glycol at 1700C, followed by reaction with 8 parts of ethylene oxide under elevated pressure 35 10 parts of diethylene glycol monobutyl ether The resulting concentrate was diluted with water in the ratio 1:9 to give the ready-to-use -4 emulsion.

*T

Claims (7)

1. Composition for the protective treatment of wood against rot and attack by insects, characterized 5 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 of water. 10

2. C mposition according to Claim 1, characterized in that it additionally comprises up to 20 parts of a polyethylene glycol compound to improve stability. 15

3. Composition according to Claim 1 or 2, charac terized in that it additionally comprises resins, binders, waxes, dyes and/or pigments.

4. Composition according to any of Claims 1 to 3, 20 characterized in that it comprises as binder at least one alkyd resin or a similar resin based on natural oils, such as linseed oil or soya oil.

5. Composition according to any of Claims 1 to 4, 25 characterized in that it comprises effective proportions of additional biocides, such as insecticides, fungicides, algicides or bactericides, to widen the activity spectrum. 30

6. Process for the protective treatment of wood, characterized in that the wood is impregnated with a composition according to one or more of Claims 1 to 5 using differences in pressure. 35

7. Process according to Claim 6, characterized in that the impregnation is carried out without heat input.