A fungicidal agent to preserve freshly cut wood against blue stain and mold fungi attacks
The present invention concerns a fungicidal agent to preserve freshly cut wood and wood products against blue stain and mold fungi attacks.
For many years pentachlorophenbl and other chlorinated phenols have been the predominant agents for preservation of cellulosic materials because of their extremely broadspectral microbiocidal effect. Chlorinated phenols have been used e.g. for combatting blue stain and mold fungi, which in particular cause discoloration of freshly cut wood. In recent years, however, it has been found that technical grade chlorinated phenols may contain traces of dioxines which are known to have teratogenic activity, just as dioxines may presumably be formed by combustion of wood which has been impregnated with chlorinated phenols.
In view of this, the use of chlorinated phenols has been prohibited in a number of countries, including Sweden, and accordingly there is an urgent need for fungicides which are not vitiated by undesirable side effects on humans and animals and which are effective against blue stain and mold fungi.
Another urgent problem is to minimize the costs and any handling and toxicity risks of wood preserving agents
The object of the present invention is to provide a fungicide of the above-mentioned type which is effective and which does not present any problems as regards human toxicity and handling.
The invention is based on the surprising finding that a mixture of two known groups of fungicidal compounds, viz.
a) urea and b) monoquatemary ammonium compounds of the type stated in the characterizing portion of claim 1 and with the restrictions stated in claim 1
exhibits a synergistic fungicidal effect against blue stain and mold fungi which, as demonstrated below, exceeds the additive effect of the individual components significantly.
The use of urea in various wood preserving compositions is generally known. Thus, the DE Patent Specification 955,551 mentions the use of urea to facilitate mouldability of mould bodies containing fungicidal wood preserving agents.
The US Patent Specification 1,921,324 mentions urea as an inflammability decreasing component of wood preserving agents on the basis of nitrophenols.
The US Patent Specification 2,347,635 concerns a synergistic mixture of urea and chlorophenols. It is stressed that though urea is considered to have fungistatic activity on fungi attacking fresh wood, urea is a suitable substrate for other microorganisms, so the use of urea may result in more serious discolorations than those caused by the mentioned fungi. This drawback is remedied, according to the patent specification, by adding chlorophenols.
A. Yde-Andersen, Det forstlige Forsogsvasen (the Danish forest reserach department) vol. XXXVIII, fascicle 3,
p. 209-17, mentions urea as an agent against attacks from the heart-rot fungus Fomes annosus (a basidiomycete), which grows only on living wood and spreads from stump faces after cutting to adjacent trees through the roots. The effect seems to be conditional upon the ability of urea to promote the growth of wood-destroying fungi, so that the stumps disintegrate faster and so that the growth of Fomes annosus is impeded.
As demonstrated below, however, urea has a very limited effect on blue stain and mold fungi.
The DE Auslegeschrift 2,132,701 describes the use of quaternary ammonium compounds of the present type in mixture with a predominant amount (70 to 93. by weight) of thiourea to combat discolouring fungi of the blue stain type. It appears from the specification that the quaternary ammonium compounds are active only in so high concentrations as 4 to 5% by weight in aqueous solution. However, as opposed to previous assumptions
(the DE Offenlegungsschrift 1,567,097), the use of thiourea is very inadvisable from an environmental point of view. Thus, the substance is toxic on aspiration, on touch of the skin and on consumption, just as it may cause allergy. Moreover, the substance is suspected of being carcinogenic, and e.g. in Norway this has caused it to be classified as a cancerogenic substance (Statens Forurensningstilsyn (the Norwegian pollution inspectorate), February 1983).
The DK Patent Specification 144,695 (of. the GB Patent Specification 1,467,420) describes the use of quaternary ammonium compounds of the present type in an aqueous system containing fungicidally active triorganotin compounds to preserve wood which has not been substantially infected by wood-destroying fungi.
A similar agent on the basis of an alkali metal salt of a biocidally active organic carboxylic acid and one or more quaternary ammonium salts of the present type is described in the DE O f fenlegungs sch rift 3,308,303, of. the FI Published Application 63,513. However, as demonstrated below, commercially available agents of this type provide poorer preservation of pine boards than the agents of the invention.
A fungicidal agent, in particular for preservation of wood, is described in the SE Published Application 425,043. In addition to a quaternary ammonium compound the agent contains at least one guanidated aliphatic diamine, such as the mixed product guazatin triacetate, and/or polyamine. However, as demonstrated below, commercially available agents of this type provide a poorer preservation, in particular of pine boards but also of spruce boards, than the agents of the invention.
Quaternary ammonium compounds of the present type are moreover mentioned briefly in "What's new in forest research", Forest Research Institute, Rotorua, New Zealand, October 77. It is concluded that these compounds have great potential as wood preservatives, but it is also emphasized that they are less useful in the treatment of freshly sawn wood. Also the effect of these compounds on blue stain and mold fungi is shown in the following test report.
The US Patent Specification 2,346,632 describes the use of e.g. urea as a consistency-imparting agent in disinfecting agents on the basis of quaternary ammonium compounds. It is said directly that the substance is indifferent and does not impair the disinfecting power.
Finally, the US Patent Specification 3, 138,533 describes
the use of a mixture of urea and quaternary ammonium compounds as a bacteriostatic and germicidal agent. The specification demonstrates a synergistic effect against the bacteria Proteus v ul ga r i s a nd St r ep t oc o cc u s pyogenes , and i t a lso r epo rt s an inhibiting effect on microorganisms (dermatophytes) which cause "Athlete's. Foot". Apart from the fact that these dermatological fungi are not related to blue stain and mold fungi, it appears clearly from the specification that urea is used partly as an "auxiliary" for the disinfecting ammonium compound, in particular as a solubility promoting agent, and partly for skin care purposes.
Conclusively, it may be said that though the quaternary aπrmonium compounds of the present type are very familiar in wood preserving agents also against blue stain and mold fungi, then there is no incitement to test mixtures with urea, in particular not when the observed very low effect of urea itself is taken into consideration. Especially, it could not be predicted that it would be possible to reduce the amount of quaternary ammonium compounds drastically to below 1. and that the mixture would be more effective than commercial synergistic mixtures containing quaternary ammonium compounds.
As mentioned, the quaternary ammonium compounds useful in the agent of the invention are defined in the characterizing portion of claim 1.
Preferred compounds within this framework are defined in claims 2, 3 and 4.
The weight proportion between urea (a) and the quaternary ammonium compound (b) can vary within the limits stated in claim 1.
The agents are preferably formulated as aqueous solutions, emulsions or suspensions.
The concentration of the constituent components depends in particular upon the microorganisms to be combatted. The values listed in the following test reports give an indication of the useful amounts in sawmill products considering that the liquid amount usually absorbed is 15 to 20 1/m3 of wood.
The fungicidal effect of the present agents and their individual components have been tested according to the standard "Mycological testing of anti-stain preservatives for freshly sawn timber. The mini-board method" NWPC Standard 1.4.1.3/79.
The samples used are freshly sawn mini-boards with the dimensions 10 x 50 x 300 mm. One half of the board is submerged for 20 sec. in the test solution (emulsion/suspension). Then the boards are sprayed with mixed spore suspensions of selected blue stain and mold fungi and after 21 days of storage in incubation boxes at room temperature the extent of fungi attacks is rated according to the following scale:
0 no fungus growth
1 traces of fungus growth
2 low fungus growth
3 moderate fungus growth 4 strong to maximum growth
(all surfaces covered)
Usually, 5 boards are used for each test solution, and a given concentration of the test compound is considered effective if the average for the treated ends is below 1.0.
The comparative compound used is sodium pentachlorophenolate and the test organisms are
Blue stain: Aureobasidium pullulans Ceratocystis pilifera Sclerophoma entoxylina
Mold fungi: Aspergillus amstelodami
Cladosporium sphaerospermum Peπicillum spp
Two test series were conducted, and the results are listed in the table below, with the. following abbreviations:
DDB didecy ldimethyl ammonium bromide DDC didecy ldimethyl ammonium chloride TCC: trimethylcoco ammonium chloride NaPCP sodium pentachlorophenolate
The above tests lead to the following conclusions:
Urea has a moderate effect when the concentration is 5% or more.
The quaternary ammonium compounds have a good effect in the concentration range of 2 to 4% by weight.
The subject mixtures of the components in which the quaternary ammonium compounds are used in concentrations considerably below the range of 2 to 4% by weight have an extremely effective preservation in accordance with the standard employed. This effect exceeds the additive effect of the compounds significantly and represents a surprising synergy.
Practice test report
To test the present wood preserving agents in practice a plurality of tests have been performed respectively by the applicant, at two Danish sawmills and at Trslaboratoriet under Statens Tekniske Forskningscentral (the wood laboratory under the state institute for technical research) in Finland.
The selected comparative compounds are partly the known agent sodium pentachlorophenolate (NaPCP) and partly a plurality of commercially available products comprised by the patent literature mentioned in the preamble to this specification.
The tests are set out in the reports below, to which the following comments may be made, it being noted in general that pine is more susceptible to attacks than spruce.
Practice test 1
It will be seen from the tests with pine and spruce stacked with intermediate sticks that the present agents 1 and 2 are better than or as good as the agents 3 and 4 of the prior art.
The improvement is even more distinct in case of pine and particularly spruce packed/stacked without intermediate sticks.
Practice test 2
It will be seen from the tests with spruce stacked without intermediate sticks that the present agent is significantly more effective than the known one.
Practice test 3
This test, which was conducted under very drastic (moist) conditions in Finland, shows that the present agent is greatly superior to the known one.
Practice test 4
This test illustrates the effectiveness of the agent.
Results of practice test 1
Wood: Pine and spruce (25x100x1000 mm) Number of samples per test: 15 Start: 03.03.84 Location: GORI, Kolding, Denmark
a) Mixture according to the DE Offenlegungsschrift 3308 303 (Na-2-E = sodiumethyl hexanoate) b) Mixture of 400 g/l (corresp. to 1.4%) benzalconium chloride and 80 g/l (corresp. to 0.3%) guazatin triacetate
(SE Published Application 425,043)
Results of practice test 2
Wood: 3 x 3" x 1.8 - 2.40 m spruce Number of samples per test: 28 Start: 15.05.84 Location: Hovborg Sawmill, Denmark
a) Mixture according to the DE Offenlegungsschrift 33 08 303
Results of practice test 3
Wood: Pine (25x100x1000 mm) Start: 13.06.84 Location: VII, Finland
c) Mixture of 33.5% Na-2-E and 18.3% TCC (i.e. 0.9% TCC), of. DE-A-33 08 303
Results of practice test 4
Wood: Spruce (75x75x2400 mm) Number of samples per test: 140 Start: 12.10.84 Location: Fuglsang Sawmill, Denmark