EP1097031A1

EP1097031A1 - Agents and method for the protective treatment of wood

Info

Publication number: EP1097031A1
Application number: EP99926219A
Authority: EP
Inventors: Hans-Norbert Marx; Tilo Vogel; Oliver Arlt; Florian Lichtenberg
Original assignee: Lonza AG; Impragnierwerk Wuelknitz GmbH
Current assignee: Lonza AG; Impragnierwerk Wuelknitz GmbH
Priority date: 1998-07-12
Filing date: 1999-07-02
Publication date: 2001-05-09
Anticipated expiration: 2019-07-02
Also published as: PL191467B1; CA2336931A1; NZ509289A; WO2000002716A1; HUP0102995A2; SK20352000A3; HU229630B1; TR200100041T2; CA2336931C; DE29923154U1; AU4356699A; ES2211097T3; HUP0102995A3; IL140666A0; PT1097031E; AU759694B2; EE04793B1; NO20010183L; PL345611A1; SK285573B6

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

Means and methods for protective treatment of wood

The present invention relates to means based on coal tar oil for the protective treatment of wood. It further relates to a method for the protective treatment of wood using the agents according to the invention.

The use of coal tar oil to protect wood against putrefaction and insect attack has been known since the mid-19th century and has been used up to the present time to preserve masts, fences, sleepers, etc. At an early stage, 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, this form of application did not lead to the desired results, so that the majority of tar oils continued to be used in the undiluted state. There have also been attempts to improve the unsatisfactory stability of coal tar oil emulsions by "homogenization" (analogous to the method used for milk) or treatment with specially adapted dispersing devices (e.g. ULTRA-TURRAX ^® ) and various additives (AT-PS- 86925, EP-A-0227430) These processes require a high level of equipment and consume a lot of energy. Recently, the application of coal tar oil emulsions in water has regained interest, in particular because in this way some disadvantages of the undiluted coal tar oil such as that unpleasant odor, the tendency to exude and the sticky surface of treated wood can be partially eliminated or reduced (US-A-5098472).

A disadvantage of this known process is the fact that the emulsions are relatively unstable and that the effective proportion of coal tar is reduced by the proportion of water and the emulsifier (s) by the emulsion, so that the amount introduced must be increased by one to ensure effective and lasting protection.

The object of the present invention was therefore to eliminate or to reduce the disadvantages of the known production processes and applications of tar oil emulsions. According to the invention, this object is achieved by the means according to claim 1 and the treatment method according to claim 6.

Surprisingly, it was found that by using biocidally active quaternary ammonium compounds, optionally with the use of polar solvents such as glycol derivatives, stable emulsions and microemulsions of coal tar oil in water can be prepared by simple stirring without special apparatus requirements. The biocidal effect of the quaternary ammonium compounds not only compensates for the dilution of the tar oil, it also shows - and this was not to be expected - that the depth of penetration and the spectrum of activity are significantly higher than that of the pure undiluted tar oil.

The agents according to the invention contain at least the following components: a) 5-90 parts, preferably 10-90 parts, coal tar oil b) 2-20 parts of a biocidal quaternary ammonium compound c) 10-90 parts water.

Here and below, all quantities are given in parts by mass.

Suitable biocidal quaternary ammonium compounds are, for example:

NC ₈ - ₂ o-alkyl-N, N-dimethyl-N-benzylammonium chloride, bromide or iodide ^ N, _N-di-C6-2 o-alkyl-N, N-dimethyl ammonium chloride, bromide or iodide 'N -Cό- ₂ o-alkyl salts ^*) of pyridine, quinoline etc. - N-C6- o-alkyl-N, N, N-trimethylammonium chloride, bromide or iodide ^*

N, N-di-C _{_6-20} alkyl-N-methyl-N-poly (oxethyl) ammonium salts'

Instead of the halides, the salts of other inorganic acids or organic carboxylic acids may also be present, e.g. B. acetate, propionate, sulfate etc.

For example, it was found that an emulsion containing only 30% tar oil, approximately 10% of a cation-active ammonium compound, approximately 5% auxiliary and 55% water was present proven to be at least twice as effective against wood-destroying fungi as undiluted, pure coal tar oil.

With the help of these funds, it is possible to use the excellent and proven long-term experience of coal tar oil and thereby the disadvantages of

Odor, sweating at high ambient temperatures, elution and the oily, sticky surface of the wood.

At the same time, a better, i.e. H. achieved a more even and deeper distribution of the protective agent in the wood, and - this appears to be particularly advantageous - the wood can have a higher moisture content than is possible when using the pure tar oil. Thus, the drying time and the drying energy for the raw wood, e.g. B. thresholds and masts, significantly lower.

Another advantage of the agents according to the invention is the fact that these in

Contrary to pure tar oil can be processed at normal ambient temperatures. Because of its viscosity and flow behavior, the pure tar oil can only be processed at temperatures around 100 ° C, combined with high energy consumption. This property of the tar oil also prevents deep penetration and optimal distribution in the wood.

The pungent smell of coal tar oil is particularly by two- and trinuclear aromatics, for. B. naphthalene and alkylnaphthalenes. These can only be partially removed by distillation, since after they have been completely removed, a tar oil with a viscosity which is too high and cannot be handled even at 100-120 ° C is formed. Due to the nature of their preparation, the agents according to the invention also allow the use of more viscous and thus highly deodorized tar oils, which also means the use of coal tar oil in sensitive areas, e.g. B. thresholds for subways, made easier or possible at all.

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

In addition to the formulation components already mentioned, the agents according to the invention can contain, for example, the following substances:

Resins, binders, polymers

Waxes

Dyes

Pigments - antioxidants

Olfactory corrections

Markers (tracer)

These preferably contain one or more constituents 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 soybean oil, in particular those which are water-soluble or water-dilutable by reaction with ethylene oxide or propylene oxide.

To broaden the spectrum of activity, the agents according to 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 can be included:

Amphoteric surfactants with a biocidal effect Methyl-benzimidazol-2-yl-carbamate 1, 2-benzisothiazolon-3 biguanides with a biocidal effect

Organic and inorganic boron compounds α-tert-butyl-α- (p-chlorophenethyl) - 1H-1, 2,4-triazole-1-ethanol 2-sec-butyl-phenyl-N-methyl carbamate (±) -cw-4- [3- (tert-Butylphenyl) -2-methylpropyl] -2,6-dimethylmo holin

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

2- (4-chlorophenyl) -3-cyclopropyl-l - (1H-1, 2,4-triazol-1-yl) butan-2-ol l- (6-chloro-3-pyridinyl) methyl-4, 5-dihydro-N-nitro-1H-imidazole-2-amine chlorhexidine and its salts

Chlorinated phenols, e.g. B. tetra and pentachlorophenol

Chloromitrobenzene derivatives l- [4- (2-chloro-α, α, α-trifluoro p-tolyloxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea l- (4-chlorophenyl) -3- (2nd , 6-difluorobenzoyl) urea α- [2- (4-chloro-phenyl) -ethyl] -α- (l, l-dimethylethyl) -lH-l, 2,4-tiiazole-l-ethanol

Cyano- (4-fluoro-3-phenoxyphenyl) methyl-3- (2,2-dichloroethenyl) -2,2-dimethylcyclopropanecarboxylate

(i? 5) -α-Cyano-3-phenoxybenzyl- (i? 5 ') - 2- (4-chlorophenyl) -3-methylbutyrate α-cyano-3-phenoxybenzyl-isopropyl-2,4-chlorophenylacetate N-cyclohexyl -N-methoxy-2,5-dimethylfuran-3-carboxamide

Di (guanidino-octyl) amine

3- (2,2-dibromovinyl-2,2-dimethyl) -α- (cyano- -phenoxybenzyl-li?, 3i?) - cyclopropanecarboxoxide

1 - [2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] - \ H- 1,2,4-triazole 1- [2- (2,4-dichlorophenyl) -4 -propyl-l, 3-dioxolan-2-yl-methyl] -lH-l, 2,4-triazole

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

3- (2,2-dichlorovinyl-2,2-dimethyl) -cyclopropane-l-carboxylic acid-α-cyano-3,3-phenoxy-benzyl ester

0, O-diethyl-0- (α-cyanobenzylidenamino) thiophosphate O, O-diethyl-O-3, 5, 6-trichloro-2-pyridyl-thionophosphate

0,0-diethyldithiophosphoryl-6-chlorobenzoxazolone

5,6-dihydro-2-methyl-l, 4-oxathiin-3-carboxanilide

NN-dimethyl-N-phenyl- (N-fluoromethylthio) sulfamide

N, N-dimethyl-N-tolyl- (N-fluoromethylthio) sulfamide O, O-dimethyl 5 '- (2-methylamino-2-oxoethyl) dithiophosphate

O, 0-dimethyl- <S- (N-phthalimido) methyldithiophosphate

3,5-dimethyl-tetrahydro-l, 3,5-thiadiazinthione- (2)

Dimethylalkylamine salts Dithiocarbamates, metal and amine salts

Ethyl 2- (4-phenoxyphenoxy) ethyl carbamate

2- (2-furanyl) - 1 H-benzimidazole

Haloacetic acids and their amides and esters 6,7,8, 9,10-hexachlor-l, 5,5a, 6,9,9a-hexahydro-6,9-methano-2,3,4-benzodioxothiepien-3-oxide

Hexachl orcy clohexane

8-hydroquinoline and its halogenated derivatives

2-iodobenzoic acid anilide 3-iodo-3-propynyl butyl carbamate

Copper-8-oxyquinoline

N-methyl-1-naphthyl carbamate

2-methyl-4-isothiazolin-3-one

Methylene bisthiocyanate Νitroalkanols with biocidal effects

N-Νitroso-N-cyclohexylhydroxylarnine and its salts

N-Νitroso-N-phenylhydroxylamine and its salts

Νorbornene-dimethanohexachlorocyclosulfite

2-N-octyl-4-isothiazolin-3-one organotin compounds, e.g. B. tributyltin oxide and tributyltin benzoate

Phenylphenols

2-isopropoxyphenyl-N-methyl carbamate

N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide

Pyridine-2-thiol-l-oxide and its salts, salicylanilide and its halogenated derivatives

(4-ethoxyphenyl) [3- (4-fluoro-3-phenoxyphenyl) propyl] - (dimethyl) silane

N- (l, l, 2,2-tetrachloroethylthio) -3,6,7,8-tetrahydrophthalimide

Tetrachloroisophthalodinitrile

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 adding binders such. B. drying alkyd resins, acrylates or other polymers, the surfaces of the treated wood can be improved mechanically and optically, combined with a further reduction in mobility (washing out and bleeding) of the coal tar oil. In contrast to coal tar oil, the systems according to the invention can furthermore be modified solely by adding dyes or pigments such that the treated wood can be colored. By adding waxes, it is possible to achieve a matt finish on the surfaces of the treated wood, combined with a strong water-repellent effect, which reduces the absorption of dripping water without hindering the moisture exchange via the vapor phase.

The preparations according to the invention are produced, for example, as follows:

(I) 5-90 parts of coal tar oil, e.g. WEI type C, are presented and, if necessary, at a slightly elevated temperature (approx. 50 ° C)

(LI) 2-20 parts of cationic surfactant, e.g. N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate, added and until

Homogeneity stirred up, then

(III) 0-20 parts of glycol derivative, e.g. B. diethylene glycol monobutyl ether, added and stirred until homogeneous, then

(IV) 0-20 parts stabilizer / solubilizer, e.g. B.) -Νonylphenol ethoxylate (EO = 10-14), added and again until

Homogeneity stirred and the mixture cooled. After cooling

(V) 10-90 parts of water are added and until a homogeneous is formed

Emulsion stirred.

This preparation forms stable, milky (opaque) or clear mixtures with low viscosity, which are introduced into the wood with good penetration without a temperature increase using a boiler pressure process (application of vacuum and pressure) can. Depending on the ratio of the formulation proportions I, U and V, the amount required for comprehensive protection of the wood is 20-80 kg / m ³ wood.

The agents according to the invention are preferably used in vacuum boiler pressure systems in such a way that the agents are introduced into the wood to be protected by means of pressure differences. The process steps include a fore-vacuum phase, a flood phase while maintaining the vacuum, and a pressure phase. If necessary, the process is completed with a final vacuum. The mass of protective agent introduced is checked by weighing. In the case of easily impregnable woods or types of wood, the water content in the compositions can be increased even further compared to the examples.

The impregnation is preferably carried out without the addition of heat, that is to say approximately at ambient temperature. As far as necessary, the water introduced into the wood with the agents can pass through

Heat treatment are withdrawn. If the preparations also contain polymers that are suitable for curing under the influence of elevated temperatures, the wood can be treated with superheated steam. This vaporization then leads to post-diffusion and more even distribution of the agents, combined with a more effective fixation. Polyethylene glycols that may be present in the preparations give them a dimensionally stabilizing effect, combined with a significantly reduced tendency of the wood treated with them to crack.

Overall, the agents according to the invention are distinguished by the following advantages compared to coal tar oil:

1. high stability of the emulsions,

2. Application possible at normal ambient temperature,

3. good distribution of protective agents, even with woods of medium moisture, 4. greatly reduced smell of the treated woods,

5. no disturbing tar oil accumulations on the treated wood,

6. greatly reduced "bleeding" of the treated wood at summer temperatures, 7. The surface structure and grain remain visible,

8. slight discoloration of the surface,

9. Compatibility with conventional lacquers and glazes,

10. significant increase in activity despite a lower content of coal tar oil in the preparations,

11. possibility of coloring the treated wood,

12.Lower leachability of the treated wood, therefore no relevant environmental pollution at the site,

13. lower toxicity compared to pure coal tar oil, 14. reduced crack formation when drying the treated wood,

1 . Possibility of using highly deodorized, highly viscous tar oils.

The following examples illustrate the composition and effect of the agents according to the invention and the implementation of the method according to the invention.

Comparative Example 1 (not according to the invention)

100 parts 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-cocoalkyl-N, N-dimethyl-N-benzylammonium acetate 4 parts nonylphenol ethoxylate (8-12 EU groups) 10 parts diethylene glycol monobutyl ether 38 parts water

Example 2

30 parts of coal tar oil

10 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium lactate

4 parts of nonylphenol ethoxylate (approx. 14 EO groups)

56 parts of water

Example 3

50 parts coal tar oil 10 parts N-cocoalkyl-N, N-dimethyl-N-benzylammonium chloride 10 parts polyethylene glycol (MW approx. 300) 30 parts water

Example 4

30 parts of coal tar oil

5 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium chloride

20 parts of diethylene glycol monobutyl ether

45 parts of water

The products designated in Examples 1-4 and Comparative Examples 1-2 were introduced into pine sapwood by means of pressure differences and the biological effect was tested in a method based on DLΝ EΝ 113. The results are summarized in Table 1 below. Table 1

Biological action against wood-destroying fungi i)

^ The basis of the evaluation were the limit values against 4 wood-destroying

Fungi after aging (EN 73) ²⁾ Coal tar oil is set to 100% in its biological effect.

It is striking that the preparations according to the invention, which are mentioned as examples 1 to 4, experience a significant increase in activity through the addition of cationic compounds, despite the lower tar oil content.

As can be seen in Table 1, the increase in effectiveness in Examples 1 to 4, based on the effective contents of coal tar oil, is 1: 3 to 1: 5.

Example 5

40 parts of coal tar oil

8 parts of N-cocoalkyl-N, N-dimethyl-N-benzylammonium acetate

4 parts nonylphenol ethoxylate (8-12 EO groups)

10 parts of diethylene glycol monobutyl ether

8 parts binder ^*)

30 parts of water

^*) Water-dilutable alkyd resin, obtained by boiling linseed oil fatty acid, pentaerythritol and polyethylene glycol (MW approx. 600). Example 6

30 parts of coal tar oil

10 parts N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium lactate 4 parts nonylphenol ethoxylate (approx. 14 EO groups)

6 parts iron oxide paste ^*) 20%

50 parts of water

^*) Pigment paste, obtained by rubbing transparent iron oxide red in polyethylene glycol (MW approx. 300)

Example 7

50 parts of coal tar oil

10 parts of N-cocoalkyl-N, N-dimethyl-N-benzylammonium chloride

10 parts of polyethylene glycol (MW approx. 300)

2 parts wax ^*)

28 parts of water

^*) Polyvinyl ether wax, warm pre-dissolved in coal tar oil

Example 8

30 parts of coal tar oil

5 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium chloride

20 parts of diethylene glycol monobutyl ether

1 part of N-methyl-1-naphthylcarbamate (Sevin) ^*) 44 parts of water

^*) pre-dissolved in tar oil Example 9

A concentrate was produced according to the following recipe:

60 parts of coal tar oil, type B WEI

20 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate

20 parts of binder made by heating 94 parts of linseed oil and

3 parts of maleic acid at 180 ° C and subsequent esterification with 3 parts of polyethylene glycol (10 EO groups) at 195 ° C

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

Example 10

A concentrate was produced according to the following recipe:

65 parts of coal tar oil, type B WEI 15 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate

15 parts of binder made by heating 92 parts of soybean oil and

3 parts maleic acid at 180 ° C and subsequent esterification with 5 parts polypropylene glycol (12 PO groups) at 170 ° C 1 part silicone defoamer 1 part propiconazole

3 parts water Example 11

A concentrate was produced according to the following recipe:

70 parts of coal tar oil, type B WEI

10 parts of N, N-didecyl-N-methyl-N-poly (oxethyl) ammonium propionate

19 parts of binder, prepared by heating 85 parts of polybutadiene oil and 5 parts of maleic acid to 150 ° C. and then esterifying with 10 parts of polyethylene glycol (10 EO groups) at 150 ° C. 1 part of oil-soluble dye

Example 12

A concentrate was produced 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 made by heating 80 parts of linseed oil and

12 parts Νeopentyl glycol at 170 ° C and subsequent reaction with 8 parts of ethylene oxide under pressure 10 parts of diethylene glycol monobutyl ether

Claims

claims

1. Agent for the protective treatment of wood against rotting and insect attack, characterized in that it contains at least the following components: a) 5-90 parts of coal tar oil b) 2-20 parts of a biocidal quaternary ammonium compound c) 10-90 parts of water.

2. Composition according to claim 1, characterized in that it additionally contains up to 20 parts of a polyethylene glycol compound to improve stability.

3. Composition according to claim 1 or 2, characterized in that it additionally contains resins, binders, waxes, dyes and / or pigments.

4. Agent according to one of claims 1 to 3, characterized in that it contains as a binder at least one alkyd resin or similar resin based on natural oils such as linseed oil or soybean oil.

5. Agent according to one of claims 1 to 4, characterized in that there are effective portions of additional biocides such as to expand the spectrum of activity

Contains insecticides, fungicides, algicides or bactericides.

6. Process for the protective treatment of wood, characterized in that it is impregnated using pressure differences with an agent according to one or more of claims 1 to 5.

7. The method according to claim 6, characterized in that the impregnation is carried out without the addition of heat.