Abstract:
Compositions for the protective treatment of wood against rot and attack by insects which comprise at least the following components: 
     a) 10-90 parts of coal-tar oil 
     b) 2-20 parts of a biocidally active quaternary ammonium compound 
     c) 10-90 parts of water. are described. The compositions according to the invention are easily preparable stable emulsions which are distinguished, inter alia, by good penetrability, strongly reduced odour of the treated woods, absence of annoying tar oil enrichments at the surface and strongly reduced “bleeding” of the treated wood at hot temperatures, considerably enhanced activity in spite of a lower coal-tar oil content and reduced toxicity compared to pure coal-tar oil.

Description:
This is a continuation of International Application No. PCT/CH99/00288, filed Jul. 2, 1999, and claims the benefit under 35 U.S.C. §119 of U.S. Ser. No. 60/158,999, filed Oct. 7, 1999, the entire disclosures of which are incorporated herein by reference. 
    
    
     FIELD OF THE INVENTION 
     The present invention relates to compositions based on coal-tar oil for the protective treatment of wood. It furthermore relates to a process for the protective treatment of wood using the compositions according to the invention. 
     BACKGROUND OF THE INVENTION 
     The use of coal-tar oil for protecting wood against rot and attack by insects has been known since the middle of the 19th century and is still customarily employed for preserving masts, fences, beams 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, 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 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 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 surface of the treated woods (U.S. Pat. No. 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 emulsifier(s), so that the amount that is applied has to be increased to ensure effective and long-lasting protection. 
     OBJECT OF THE INVENTION 
     Accordingly, it was an object of the present invention to eliminate or reduce the disadvantages of the known preparation processes and applications of tar oil emulsions. 
     According to the invention, this object is achieved by the compositions described below and pressure treating wood with a composition of the present invention. 
     SUMMARY OF THE INVENTION 
     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 stable emulsions and microemulsions of coal-tar oil in water by simple stirring without any special equipment requirements. Not only does the biocidal action of the quaternary ammonium compounds compensate for the fact that the tar oil is diluted, but it has additionally 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: 
     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. 
     Here and below, all amounts are stated in parts by mass. 
     Suitable biocidally active quaternary ammonium compounds are, for example: 
     N—C 8-20 -alkyl-N,N-dimethyl-N-benzylammonium chloride, bromide or iodide *)    
     N,N-di-C 6-20 -alkyl-N,N-dimethylammonium chloride, bromide or iodide *)    
     N—C 6-20 -alkyl salts *)  of pyridine, quinoline, etc. 
     N—C 6-20 -alkyl-N,N,N-trimethylammonium chloride, bromide or iodide *)    
     N,N-di-C 6-20 -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 acids to be present, for example acetate, propionate, sulphate, etc. 
     It has been found, for example, that an emulsion comprising only 30% of tar oil, about 10% of a cationic ammonium compound, about 5% of auxiliary 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 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 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 wood, for example beams and masts, can be reduced considerably. 
     DETAILED DESCRIPTION OF THE INVENTION 
     A further advantage of the compositions according to the invention consists in the fact that they can be processed at normal ambient temperatures, 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° C., which is associated with a high energy input. Moreover, this property of tar oil stands in the way of deep 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 they are removed completely, a tar oil is formed which has a viscosity which is too high and not even manageable at 100-120° 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 high viscosity which, accordingly, are highly deodorized, which facilitates the use of coal-tar oil even in sensitive areas, for example beams for underground rails, or makes this use possible in the 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 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 monobutyl ethers. 
     In addition to the formulation components already mentioned, the compositions according to the invention may comprise, for example, the following substances: 
     resins, binders, polymers 
     waxes 
     dyes 
     pigments 
     antioxidants 
     odour-masking substances 
     markers (tracers) 
     They preferably comprise one or more components from the group of the resins, binders, waxes, dyes and pigments. 
     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. 
     To widen the activity spectrum, the compositions according to the invention preferably additionally comprise an effective amount of one or more insecticides, fungicides, algicides or bacteriocides. 
     They may comprise, for example, one or more of the following active compounds: 
     Amphoteric surfactants having biocidal action 
     Methyl benzimidazol-2-ylcarbamate 
     1,2-Benzisothiazol-3-one 
     Biguanides having biocidal action 
     Organic and inorganic boron compounds 
     α-tert-Butyl-α-(p-chlorophenethyl)-1H-1,2,4-triazol-1-ethanol 
     2-sec-Butylphenyl N-methylcarbamate 
     (±)-cis-4-[3-(tert-Butylphenyl)-2-methylpropyl]-2,6-dimethylmorpholine 
     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 salts 
     Chlorinated phenols, for example tetra- and penta-chlorophenol 
     Chloronitrobenzene derivatives 
     1-[4-(2-Chloro-α,α,α-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-triazol-1-ethanol 
     Cyano(4-fluoro-3-phenoxyphenyl)methyl 3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate 
     (RS)-α-Cyano-3-phenoxybenzyl-(RS)-2-(4-chlorophenyl)-3-methylbutyrate 
     α-Cyano-3-phenoxybenzyl isopropyl-2,4-dichlorophenylacetate 
     N-Cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide Di(guanidinooctyl)amine 
     3-(2,2-Dibromovinyl-2,2-dimethyl)-α-(cyano-m-phenoxy-benzyl-1R,3R)cyclopropanecarboxylate 
     1-[2-(2,4-Dichlorophenyl)-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole 
     1-[2-(2,4-Dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-1,2,4-triazole 
     3-Phenoxybenzyl (+)-3-(2,2-dichlorovinyl-2,2-dimethyl)-cyclopropane-1-carboxylate 
     α-Cyano-3,3-phenoxybenzyl 3-(2,2-dichlorovinyl-2,2-dimethyl)cyclopropane-1-carboxylate 
     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-oxathiine-3-carboxanilide 
     N,N-Dimethyl-N′-phenyl-(N′-fluoromethylthio)sulphamide 
     N,N-Dimethyl-N′-tolyl-(N′-fluoromethylthio)sulphamide 
     O,O-Dimethyl-S-(2-methylamino-2-oxoethyl) dithiophosphate 
     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 
     2-(2-Furanyl)-1H-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 
     8-Hydroxyquinoline and its halogenated derivatives 
     2-Iodobenzanilide 
     3-Iodo-3-propinyl butylcarbamate 
     Copper 8-oxyquinoline 
     1-Naphthyl N-methylcarbamate 
     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 
     Norbornene dimethanohexachlorocyclosulphite 
     2-N-Octyl-4-isothiazolin-3-one 
     Organotin compounds, for example tributyltin oxide and 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 
     Tetrachloroisophthalonitrile 
     2-(Thiazol-4-yl)benzimidazole 
     2-Thiocyanomethylthiobenzothiazole 
     1-(1,2,4-Triazol-1-yl)-1-(4-chlorophenoxy)-3,3-dimethylbutan-2-ol 
     1-(1,2,4-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 
     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 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 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 prepared, for example, as follows: 
     (I) 5-90 parts of coal-tar oil, for example WEI type C, are initially charged and, if appropriate at slightly elevated temperature (about 50° C.), admixed with 
     (II) 2-20 parts of cationic surfactant, for example N,N-didecyl-N-methyl-N-poly-(ethoxy)ammonium propionate, and the mixture is stirred until homogeneity is achieved; 
     (III) 0-20 parts of glycol derivative, for example diethylene glycol monobutyl 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 (EO=10-14), are then added and the mixture is once more stirred until homogeneity is achieved, and the batch is cooled. After cooling, 
     (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 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 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 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 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. 
     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 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 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 to crack. 
     Altogether, the compositions according to the invention have the following advantages compared with coal-tar oil: 
     1. high stability of the emulsions, 
     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 wood, 
     6. strongly reduced “bleeding” of the treated wood at hot temperatures, 
     7. the surface structure and the grain remain visible, 
     8. only slight discoloration of the surface, 
     9. compatibility with customary varnishes and clearcoats, 
     10. considerably enhanced activity in spite of a lower content of coal-tar oil in the preparations, 
     11. option to stain the treated woods, 
     12. less leaching of the treated woods, and consequently no relevant local environmental stress, 
     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 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) 
     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 
     10 parts of anionic emulsifier 
     40 parts of water 
     EXAMPLE 1 
     40 parts of coal-tar oil 
     8 parts of N-cocosalkyl-N,N-dimethyl-N-benzylammonium acetate 
     4 parts of nonylphenol ethoxylate(8-12 EO groups) 
     10 parts of diethylene glycol monobutyl ether 
     38 parts of water 
     EXAMPLE 2 
     30 parts of coal-tar oil 
     10 parts of N,N-didecyl-N-methyl-N-poly(ethoxy)ammonium lactate 
     4 parts of nonylphenol ethoxylate (about 14 EO groups) 
     56 parts of water 
     EXAMPLE 3 
     50 parts of coal-tar oil 
     10 parts of N-cocosalkyl-N,N-dimethyl-N-benzylammonium chloride 
     10 parts of polyethylene glycol (MW about 300) 
     30 parts of water 
     EXAMPLE 4 
     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 
     45 parts of water 
     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. 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Biological action against wood-destroying fungi 1)   
               
             
          
           
               
                   
                 Tar oil content 
                 Relative activity 2)   
               
               
                 Example No. 
                 [%] 
                 [%] 
               
               
                   
               
             
          
           
               
                 C1 
                 100 
                 100 
               
               
                 C2 
                 50 
                  &lt;50   
               
               
                 1 
                 40 
                 130 
               
               
                 2 
                 30 
                 145 
               
               
                 3 
                 50 
                 165 
               
               
                 4 
                 30 
                  90 
               
               
                   
               
               
                   1) Evaluation was based on the limit values against 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 to the invention mentioned as Examples 1 to 4 have 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 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 
     8 parts of N-cocosalkyl-N,N-dimethyl-N-benzylammonium acetate 
     4 parts of nonylphenol ethoxylate (8-12 EO groups) 
     10 parts of diethylene glycol monobutyl ether 
     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) 
     EXAMPLE 6 
     30 parts of coal-tar oil 
     10 parts of N,N-didecyl-N-methyl-N-poly(ethoxy)ammonium lactate 
     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 iron oxide in polyethylene glycol (MW about 300) 
     EXAMPLE 7 
     50 parts of coal-tar oil 
     10 parts of N-cocosalkyl-N,N-dimethyl-N-benzylammonium chloride 
     10 parts of polyethylene glycol (MW about 300) 
     2 parts of wax *)    
     28 parts of water 
       *)  Polyvinyl ether wax, pre-dissolved in hot coal-tar oil 
     EXAMPLE 8 
     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 (Sevin) *)    
     44 parts of water 
       *)  pre-dissolved in tar oil 
     EXAMPLE 9 
     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 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) at 195° C. 
     The resulting concentrate was diluted with water in the ratio 1:9 to give the ready-to-use emulsion. 
     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-poly (ethoxy)ammonium propionate 
     15 parts of binder, prepared by heating 92 parts of soya oil and 3 parts of maleic acid at 180° C., followed by esterification with 5 parts of polypropylene glycol (12 PO groups) at 170° C. 
     1 part of silicone antifoam 
     1 part of propiconazole 
     3 parts of water 
     EXAMPLE 11 
     A concentrate was prepared according to the following recipe: 
     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 maleic acid at 150° C., followed by esterification with 10 parts of polyethylene glycol (10 EO groups) at 150° C. 
     1 part of oil-soluble dye 
     The resulting concentrate was diluted with water in the ratio 1:9 to give the ready-to-use emulsion. 
     EXAMPLE 12 
     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 
     19 parts of binder, prepared by heating 80 parts of linseed oil and 12 parts of neopentyl glycol at 170° C., followed by reaction with 8 parts of ethylene oxide under elevated pressure 
     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 emulsion.