DD275433C2 - NEW WOOD PROTECTION - Google Patents

Description

Field of application of the invention

The invention relates to novel wood preservative active ingredients for oily wood preservative formulations for the comprehensive protection of HnIz against wood-discoloring and wood-destroying fungi.

Characteristic of the known technical solutions

For the protection of wood against fungi a variety of active ingredients are known. In practical Holzachutz but only a very limited number of substances use, since the complicated synthesis of new drugs often requires an unreasonably high economic cost and a special raw material base.

The following are used in particular: tributyltin oxide, pentachlorophenol, dichlofluanid and methylbisbisrhodanide.

Tributyltin oxide is a long-standing proven wood preservative active ingredient, which degrades very rapidly on UV irradiation and thus can not guarantee effective protection against wood-discolouring fungi.

Although pentachlorophenol has a comprehensive and long-lasting effect against wood-discoloring as well as against wood-destroying fungi, but is because of its persistence and the by-product contained as environmental poison under criticism. In practice, the agent must be used in relatively high concentrations (4 to 8% solutions) to counteract degradation by UV radiation.

Dichlofluanid is effective against wood-discoloring fungi, but its low activity against wood-destroying fungi requires fairly high levels of application. In addition, this drug is not stable to UV radiation.

Methyiene bisrhodanide is effective against wood-discoloring fungi but not generally applicable for toxicological reasons. Also combinations o.g. Active ingredients have not solved these problems. The durability of the wood is impaired by the rapid degradation of the active ingredients on the wood surface, resulting in an infestation with wood-discoloring and wood-destroying fungi.

In DD-PS 154957 and 155001 new wood preservatives or wood coatings are described, which are characterized by a wide range of uses, extended duration of action and good fungicidal activity. They contain active ingredient combinations of tributyltin compounds, tributyltin dialkyldithiocarbamates and tetraalkylthiuram disulfide.

A disadvantage of this wood preservative combination is the relatively high application rate and the associated toxicity problems.

Object of the invention

The object of the invention is to find new less toxic UV-stable wood preservative active ingredients with a comprehensive action against wood-discoloring and wood-destroying fungi which can be used alone or in combination with other active ingredients.

Explanation of the essence of the invention

The object of the invention is to find new, easily accessible and easy to produce active ingredients that are suitable for effective wood protection.

This object is according to the invention dadurct, solved that the new wood preservatives in addition to conventional excipients and carriers as active compounds of the general formula

XCH ₀ S

^ RS

in the

R is a lower alkyl or alkylene radical or an aralkyl radical and X is halogen.

The new active compounds can be prepared by literature methods (DD-PS 256693) by alkylation of potassium monoester salts of Cyanimidodithiokohlensäure with chlorobromoethane and optionally subsequent Umhalogenierung.

Surprisingly, they are outstandingly effective against wood-discolouring and wood-destroying fungi. The effect of the invention against wood-destroying fungi already occurs at concentrations of <0.34 kg / m ³ . The active ingredients are less toxic and readily soluble in commercial organic solvents. They penetrate very well into the wood and thus guarantee a deep protection of the treated material. This is particularly significant because such agents, which adhere only to the surface, can not protect the wood from cracking in the presence of a fungicidal attack. The wood preservatives of the invention may in addition to conventional organic solvents and hydrophobizing additives in amounts of 1-10% by weight in the form of solid paraffins, chlorinated paraffins or silicone oils and / or 0.5 to 20% by mass of binder such as linseed oil, Leinölfirniß , Alkyd resins, vinyl resins, chlorinated vinyl resins or / and in the respective solvent mixture-soluble polymeric substances such as resins, bitumen or tar oils. For practical purposes, taking into account the requirements in terms of long-term effects and safety wood preservatives according to the invention contain at least one or two of the active compounds according to the invention in concentrations of 0.1-10%, preferably 0.2-3%. The wood preservatives according to the invention may additionally contain known wood preservatives such as tributyltin oxide, tributyltin benzoate, pentachlorophenol, dichlofluanid, methylenebisrhodanide and / or others.

Ausführungsbel-plele

In the following, the invention will be explained by way of example without limiting it.

The results are presented in the form of tables showing the respective active substances used and the concentrations used, as well as the rating. In addition, some wood preservative formulations have been used in these tests, which are subsequently referred to by their short names. The test is carried out in the concentration indicated according to the test description.

Recipe 1

Chloromethyl ethyl cyanimidodithiocarbonate 2%

Chlorobenzene 10%

p-chlorobenzene 20%

o-dichlorobenzene 20%

Gasoline 140/180 48%

Recipe 2 chloromethyl-n-propyl cyanimidodithiocarbonate 1.8%

Chlorobenzene 5%

p-dichlorobenzene 10%

o-dichlorobenzene 30%

Petrol 140/180 '45.2%

Heavy oil 8%

Recipe 3 chloromethyl-iso-propyl-cyanimidodithiccarbonate 2%

petrol 40% Chloromethyl-methyl-cyanimidodithiocarbonat Recipe 5 10% Allyl chlorrnethyl-cyanimidodithiocarbonat 5% paraffin 5% toluene 76% vinyl resin 1% montan resin 5% petrol 10% silicone oil 23.2% xylene 48% linseed oil 3% petrol 70% Recipe 4 alkyd resin 0.5% xylene desiccant

0.5%

0.8%

Recipe β

Benzyl chloromethyl cyanimidodithiocarbonate 1%

Polystyrene 2%

Xylene 50%

Parprfin 2%

Silicone oil 1%

Chlorobenzene 10%

o-dichlorobenzene 11%

p-dichlorobenzene 23%

Recipe 7 chloromethyl-methyl-cyanimidodithiocarbonate 0.5%

Tributylzlnnoxid Pentachlorophenol 0.8% chlorobenzene chlorobenzene 15% p-Dichlorbonzol p-dichlorobenzene 20% o-dichlorobenzene o-dichlorobenzene 25% chlorinated polyethylene chlorinated polyethylene 3% Gasoline 140/180 Gasoline 140/100 30.7% xylene xylene 5% Recipe 8 4.3% 15% 20% 22% 3% 30.7% 5%

example 1

Testing against wood-discolouring fungi Experiment description

Groundwood paperboard measuring 4.5 × 13.4 cm is impregnated with 2.12 g test solution in the concentration indicated and dried. Subsequently, the boards were loaded in the Xenon tester with UV radiation. The load takes place in several stages. After this treatment, the cardboard must be moistened before the biological test. The inoculation is carried out with a spore suspension of the test fungus Pullularia pullulans. The inoculated cardboard is placed in a humid chamber for incubation and stored at a temperature of 20 to 26 ° C in the incubator. The evaluation takes place after 10 days.

rating scale:

1 = heavy infestation

2 = average infestation

3 = low infestation

4 = no infestation

Table 1 summarizes the results obtained:

Table 1 Inhibition of wood-discoloring fungi by the agents according to the invention

(known) Wirkstoffkonz. UV- Load in h - 4 - 285 433 active substance tributyltin in% 0 100 tributyltin _ 1 1 200 300 untreated Pentachlorophenol 1 1 (Invention) Tributyltin oxide / thiuram 0.1 4 4 Chloromethyl-ethyl-cyanimidodithiocarbonat Tributylzinndimethyldithiocarbamat / thiuram 0.05 4 4 4 • i 0.01 4 4 4 4 0.1 4 4 4  1 Chloromethyl-n-propyl-cyanimidodithiocarbonat 0.05 4 4 4 4 0.01 4 4 4 4 0.1 4 4 4 4 Chloromethyl-iso-propyl-cyanimidodithiocarbonat 0.05 4 4 4 4 0.01 4 4 4 4 0.1 4 4 4 4 Allyl chloromethyl-cyanimidodithiocarbonat 0.05 4 4 4 4 0.01 4 4 4 4 0.1 4 4 4 4 Benzyl-chloromethyl-cyanimidodithiocarbonat 0.05 4 4 4 4 0.01 4 4 4 4 0.1 4 4 4 4 Chloromethyl-methyl-cyanimidodithiocarbonat 0.05 4 4 4 4 0.01 4 4 4 4 4 4 Tributyltin oxide / + chloromethyl-methyl 0.3 / 0.05 4 4 cyanimidodithiocarbonat 4 4 4 4 Recipe 1 4 4 4 4 2 4 4 4 4 3 4 4 4 4 4 4 4 4 4 5 4 4 4 4 6 4 4 4 4 7 4 4 0.3 4 3 0.1 4 1 1 1 5 4 3 1 1 0.1 / 0.3 4 4 3 2 0.1 / 0.3 4 4 4 4 4 4

Example 2

Protective effect of the agents according to the invention against wood-destroying fungi in the full-pot process trial shelling

Holzklötzchen test specimens were loaded in a full-dousing process with different amounts of the listed formulations.

Part of the specimens were then subjected to leaching by water storage. Subsequently, all specimens were exposed to attack by fungi from the group of Basidiomycetes or Ascomycetes.

Table 2 shows the limit values in kg total active substance / m ³ wood, which reliably prevent fungal attack of the specimens.

This means o. A. without, m. A. with water leaching.

Table 2

Limiting values (kg / m ³ wood) of the growth inhibition of wood-destroying fungi on wooden block test specimens in the full impregnation process with the compositions according to the invention

active substance (known) Coniophora puteana test fungi globosum Recipe 8 O.A. M.A. Chaetomium M.A. O.A. (Invention) 0.25 0.20 2.3 Recipe 1 0.19 0.20 1.09 2.4 2 0.34 0.30 1.20 2.2 3 0.25 0.26 1.18 2.2 4 0.30 0.30 1.31 2.0 5 0.34 0.30 1.40 2.1 ß 0.24 0.24 1.11 0.7 7 0.70 1.05 1.48 3.5 1.4

-5- 285 433

Example 3 Protection of the agents according to the invention against wood-discolouring fungi in the paint process Versuci.sbeschreibung Wooden boards were mixed with 100g m ^{2 of} a solution containing different concentrations of the active compounds of the invention

contained, deleted. After drying the paint, a part of the test pieces was subjected to 135 hours of water suction. All boards were then exposed to the attack of the test fungus Aurobasidium pullulans.

Table 3 summarizes the results (rating scheme see Example 1). Table 3 Growth inhibition of the compositions of the invention in wood-discoloring fungi in the paint process

active substance concentration test fungus Aurobasidium pullulans g / m ² O.A. M.A. untreated - 1 1 (Erfindurgsgemäß) Chloromethyl-methyl-cyan 0.5 4 3-4 imidodithiocarbonat 1.0 4 3-4 2.0 4 4 3.0 4 4 4.0 4 4 Chloromethyl-n-propyl-cyan 0.5 4 3-4 imidodithiocarbonat 1.0 4 4 2.0 4 4 3.0 4 4 4.0 4 4 Chloromethyl-ethyl-cyan 0.5 4 3-4 imidodithiocarbonat 1.0 4 3-4 2.0 4 4 3.0 4 4 4.0 4 4 (known) Pentachlorophenol 0.5 1 1 1.0 1-2 1 2.0 3 1 3.0 4 1-2 4.0 4 2 6.5 4 4

Claims (4)

1. New wood preservatives with a broad spectrum of activity, preferably against wood-destroying and especially holzverfärbende mushrooms, characterized in that they are in addition to conventional Forniulierungshilfsstoffen as active ingredients cyanimidodithiocarbonates of the general formula XCH ₂ S G = N-GSN,
RS " in which R is a lower alkyl, alkenyl or aralkyl radical and X is halogen. 2. New wood preservatives according to claim 1, characterized in that they contain the active ingredients in concentrations of 0.01-10 parts by weight in%. 3. New wood preservative according to claim 1, characterized in that they contain the active ingredients alone or in combination with other known wood preservative active ingredients. 4. novel wood preservative according to claim 1, characterized in that they in addition to conventional organic solvents hydrophobizing additives in amounts of 1-10 parts by weight in% in the form of solid paraffins, chlorinated paraffins or silicone oil and / or 0.5-20 parts by weight in% binder such as linseed oil, Linseölfirniß, alkyd resins, vinyl resins, chlorinated vinyl resins and / or soluble polymeric substances such as resins, bitumen or tar oils.