DD155001B1 - WOOD PROTECTIVE PAINTINGS - Google Patents

Abstract

The invention relates to paints with holzschützendem character in which novel drug combinations were used. In particular, for outdoor use to protect wood and materials from wood against damage from biological attack and weathering of the wood surface, the paints are used. They contain active substances from at least two of the classes of compounds tributyltin compounds, tributyltin dialkyldithiocarbamates and tetraalkylthiuram disulfides.

Description

Field of application of the invention

The invention relates to paints with novel drug combinations, especially for outdoor use, mainly for the protection of wood and wood materials against damage from biological attack and weathering of the wood surface.

Characteristic of the known technical solutions

The equipment of paints with active ingredients having predominantly fungicidal activity has only recently acquired technical importance after it has been recognized that biological damage factors are substantially involved in the premature destruction of exterior paints on organic paints, especially wood. The experience gained in the meantime shows that the known technical solutions, especially with regard to the spectrum of activity, the duration of efficacy and the toxicological properties, do not meet all the requirements of the conditions of use.

For paints on wood and other paints, containing food sources for microorganisms find as organic fungicides pentachlorophenol, organic copper compounds, tributyltin compounds and increasingly dichloro-luantide (N-dimethylamino-N-phenyl-N'-fdichlorfluormethylmercaptol-sulfanid) use. Pentachlorophenol must be used in high concentrations, does not have sufficient UV stability and should be regarded as an environmental toxin because of possible highly toxic contaminants and its slow degradation.

Organic copper compounds are sufficiently effective in high concentrations, but can only be used for special purposes because of the non-consistent green inherent color.

Tributyltin compounds are effective only in high dosage due to the limited UV stability with otherwise good leaching resistance, which leads to the reduction of efficiency and toxicological problems. Especially against wood-discolouring fungi, the most essential biological paint destroyer, they only achieve satisfactory effect with otherwise good protective effect against wood-destroying basiomycetes and moder fungus pathogens.

Although dichlofluanid has a good effect on wood-discolouring fungi, it is not stable to hydrolysis in aqueous medium, is not UV-stable and must be used in high concentrations because of the low activity against Basidiomycetes and moder rot pathogens, which leads to a reduction in cost-effectiveness.

Combining these agents does not solve the problem because it does not eliminate UV instability. Especially this rapid reduction of active ingredient on the surface of the materials leads to inefficiency against wood-discolouring fungi at low concentrations of active ingredient, which usually strive for the known technical solutions, although the stability of the organic support made of wood or cellulose is initially not affected, but the adhesion and durability of the Paint films are significantly reduced. It comes thereby to the flaking of the film and with fluctuating dampness shrinkage cracks form in the wood, which form a point of attack for wood-destroying mushrooms. In the case of modern wood stains, this phenomenon is even more critical because, due to the lower binder and pigment content, the effect of UV increases. The thin film, which is partially permeable to water, but represents just the main advantage over conventional paints, since only so the flaking of the film and extensive work on indispensable renewal coatings are avoided.

Object of the invention

The aim of the invention is the production of paints, based on drug combinations with significantly improved UV stability, a thorough improvement of the protective effect of wood preserving paints against the totality of wood-damaging fungi with low active ingredient use, reduced harmful load, high efficiency and improvement of the technical equipment Effect properties.

Explanation of the essence of the invention

The technical task was the development of wood preserving paints or primers, which increase the durability of the paint film at low concentrations of active substance and, up to the renewal, the protection of the materials underneath, especially wood and materials made of wood against the damage caused by biological attack and weathering Ensure wooden surface.

It has now been found that, surprisingly, tetraalkylthiuramidesulfides, in particular tetramethylthiuram disulfide (thiuram), which are non-toxic as gum aides, less toxic plant fungicides with very short waiting time and fungicide for the preservation of various organic materials, but which are unlikely to protect wood and wood materials because of UV instability Use found in inventive combination with Tributylzinnverbindungen in paints an excellent effect especially on the surface of wood and wood-based materials unfolded. This can lead to a reaction between the active ingredients to Tributylzinndialkyldithiocarbamaten, so that the combinations of the invention consist of 2 to 3 active ingredients. The outstanding effect is particularly noticeable after UV exposure. While in the known technical solutions and when using Tetraalkylthiuramdisulfiden the effect after UV exposure in the test fungi greatly diminishes or only in disproportionately high amounts is sufficient, shows a completely different picture in combinations according to the invention. The effect is fully preserved against all wood-discoloring and wood-destroying fungi. It comes in addition to a synergistic effect, so that the effect is further increased. On the basis of this combination of active ingredients, it is thus possible to produce coatings containing active substance with relatively low total active substance combinations with all-round protective effects. The active ingredient combinations are dissolved, emulsified or suspended in paints of conventional type.

The UV resistance is of particular importance for inventive most pigmented glazes, since in this case the biological protective function is of particular importance. The new paint! I am a depot that ensures protection even over a certain distance (cracks).

The invention thus develops its particular quality especially in primers and glazes and is preferred for use. The effect of the invention occurs even at low concentrations, combinations of 0.1% Tributylzinnverbindungen with 0.01% Tributylzinndialkyldithiocarbamaten and / or 0.01% Tetraalkylthiuramdisulfid, in particular Tetramethylthiuramdisulfid in question.

As tributyltin compounds z. For example, tributyltin oxide, tributyltin carboxylates of any kind, which may also be polymeric, tributyltin sulfide, tributyltin fluoride suitable as Tributylzinndialkyldithiocarbamate are especially Tributylzinndimethyl- and diäthyldithiocarbamat into consideration and as tetraalkylthiuramides especially tetramethyl and ethylthiuram disulfide can be used.

As binders for the paints according to the invention can be virtually all conventional binders alone or in combinations such. B. ' all types of alkyd resins, vinyl resins, chlorinated vinyl resins, especially in combination with linseed oils and alkyd resins, but also particularly aqueous dispersion types based on polyvinyl acetate and polyvinyl acrylates can be used. The amount of binder depends on the objective of the coating film formation.

To improve the effect, to fix the active ingredient, to stabilize the wood and to improve the adhesion and durability of the paint film in addition also appropriate organic and / or inorganic pigments, plasticizers, water repellents, stabilizers, solvents and diluents are added.

When using alkyd resins and drying oils, it is advantageous to use the tributyltin compounds in at least double or higher amounts, based on molecular weights, relative to tetraalkylthiuram disulfides.

For practical purposes, taking into account the duration of action are concentrations of 0.1 to 3, preferably 0.5 to 2% Tributylzinnverbindungen with 0.01 to 3, preferably 0.05 to 2% Tributylzinndialkyldithiocarbamaten and / or 0.01 to 3, preferably 0 , 2 to 1% Tetraalkylthiuramdisulfiden used.

embodiment

The invention will be explained below with reference to several examples without wishing to restrict it.

example 1

Effect of Inventive Drug Combinations Compared to Known Solutions Against Test Mushrooms Experimental Description:

Groundwood cardboard measuring 4.5 x 13.4 cm is impregnated with 2.12 g sample solution in the specified concentration and dried. The boards are then exposed to UV radiation in the xenon tester. The load takes place in several stages. After this treatment, the cardboard must be moistened before the biological test. Inoculation takes place with a spore suspension. The inoculated cardboard is placed in a moist chamber for incubation and stored at a temperature of 20 ⁰ C to 26 ° C in the incubator. The evaluation takes place after 10 days.

Boniturschema: 1 = heavy infestation

2 = average infestation

3 = low infestation 4 = no infestation

concentration UV exposure in h 100 -3- 200 155 001 Test fungus: Pullularia pullulans 0 3 1 active substance 0.4 4 3 3 2.0 4 4 4 300 tributyltin 0.1 / 0.3 4 3 2 1 Pentachlorophenol 0.5 4 2 Tributyltin oxide / thiuram 4 4 4 thiuram 0.2 / 1 4 2 Tributylzinnsalizylat / 4 4 thiuram 0.1 / 0.3 4 4 Tributylzinndimethyldithio- 4 4 carbamate / thiuram 0.15 / 0.4 4 4 Tributyltin oxide / tributyltin diethyldithiocarbamate 4 4 4 Tributyltin oxide / tributyl 0.2 / 0.1 / 0.1 4 zinndimethyldithiocarbamat / thiuram 4

Test fungus: Ceratocystis spec.

Tnbutylzinnoxid / tributyl 0.05 / 0.5 4 4 4 4 zinndiäthyldithiocarbamat 0.08 / 0.4 4 4 4 4 Tributylzinnsulfid / thiuram 0.8 4 4 3 2 dichlofluanid Tributylzinndimethyldithio- 0.1 / 0.5 4 4 4 4 carbamate / thiuram Tributyltin oxide / tributyltin 0.05 / 0.3 4 4 4 4 dimethyldithiocarbamate Tributylzinndiäthyldithio- 0.2 / 0.4 4 4 4 4 carbamate / Tributylzinnsulfid 0.8 4 2 1 1 thiuram 0.6 4 4 2 1 tributyltin Test fungus: Alternaria humincola 0.4 4 3 2 2 tributyltin 0.2 / 0.5 4 4 4 4 Tributyltin oxide / thiuram 0.1 / 0.3 4 4 4 4 Tributylzinnazetat / thiuram 0.3 / 0.1 4 4 4 4 Tributylzinnbenzoat / thiuram

Tributyltin dimethyldithiocarbamate / thiuram Tributyltin oxide / Tnbutylzinndiäthyldithiocarbamat

Test fungus: Scopularia phycomyces

thiuram

Tributyltin diethyldithiocarbamate / tetraethylthiuram disulfide

Tributyltin oxide / tetraethylthiuram disulfide pentachlorophenol tributyltin oxide / pentachlorophenol

0.1 / 1

0.2 / 0.4

0.5

0.1 / 0.3

0.1 / 0.3

0.2 / 3

Example 2

Testing of inventive and comparative paints against test fungi

Test Description:

Wood panels are provided on all sides with the paint to be tested, dried and exposed in the xenon test with various doses UV radiation. Subsequently, the specimens are sterilized with propylene oxide. Beforehand, sterilized collagen 75 ml of nutrient medium are introduced, followed by inoculation with the appropriate spore suspensions.

It is incubated at about 22 ⁰ C for 7 days. In these collars small glass benches are placed, then the sterilized specimens are placed and incubated at 22 ° C for 3 to 4 weeks depending on the fungus species. Afterwards is scored.

Formulation of the tested paints (in%)

1) tributyltin oxide 0.2 tributyltin dimethyldithiocarbamate 1.0 alkyd resin 10 linseed oil 5 gasoline 140/180 42.8 paraffin 1 xylene 40

2) Tributyltin oxide 0.8 Tributyltin dimethyldithiocarbamate 0.2 Thiuram 0.2 Vinyl resin 15 Paraffin 1 Silicone oil 1 Xylene 81.8

3) tributyltin diethyldithiocarbamate 0.3 thiuram polyvinyl acetate latex 70 water 28.7

4) tributyltin benzoate 0.8 thiuram 0.2 polyacrylate latex 50 water 49

5) tributyltin oxide 1.0 thiuram 0.5 polyacrylate latex 60 water 38.5

6) pentachlorophenol 1 linseed oil 10 gasoline 89

7) Tributyltin oxide 1 Linseed oil 10 Gasoline 89

8) Dichlofluanid 0.6 Linseed oil 10 Gasoline 89.4

9) thiuram 0.9 polyvinyl acetate latex 60 water 39.1

10) Tributyltin oxide 1 Thiuram 1 Chlorinated vinyl resin 5 Paraffin 2 Iron oxide Red 5 Xylene 76 Alkyd resin 10

11) Tributyltin oxide 1 Thiuram 1 Chlorinated polyethylene 15 Paraffin 1 Iron oxide yellow 5 Xylene 72 Linseed oil 5

Test fungus: Alternaria humincola

Recipe UV exposure in h

0 100 200 300_

1 4 4 4

2 4 4 4

3 4 4 4

4 4 4 4

5 4 4 4

6 4 2 2

7 4 3 2

8 4 4 3

Test fungus: Scopularia phycomyces recipe

UV load in h 0 100

200

300

1 4 4 100 100 100 4 4 2 4 4 4 4 4 4 4 3 4 4 3 4 4 4 4 4 4 4 2 4 4 4 4 5 4 4 4 4 4 4 4 6 4 4 4 4 4 2 2 7 4 2 4 4 3 2 1 Test fungus: Puilularia pullulans 4 2 2 recipe UV exposure in h 4 4 4 0 4 4 200 300 6 4 UV exposure in h 2 1 7 4 0 UV exposure in h 2 1 9 4 4 0 2 1 1 4 4 4 4 4 2 4 .4 4 4 4 3 4 4 4 4 4 4 A 4 4 4 4 5 4 4 4 4 4 Test fungus: Ceratocyctis spec. 4 4 recipe 4 4 4 4 200 300 1 4 4 4 2 4 4 3 4 4 4 4 4 5 4 4 6 2 2 7 2 2 8th 2 1 10 4 4 Test fungus: Altemaria tenuis recipe 200 300 1 4 4 2 4 4 3 4 4 4 4 4 5 4 4 6 1 1 7 2 1 10 4 4 11 4 4

Test fungus: Coniophora puteana recipe

UV load in h 0 100

4 4 4 4 4 4 4 4 4

200

4 4 4 4 4 2 2 4 4

300

4 4 4 4 4 2 1 4 4

Testpiiz: Chaetomium globosum recipe

UV load in h 0 100

200

300

1 2 3 4 5 6 7 10

Test mushroom: Androdia sinuosa recipe

4 4 4 4 4 3 4 4

4 4 4 4 4 2 4 4

UV load in h 0 100

4 4 4 4 4 2 3 4

200

4 4 4 4 4 1 1 4

300

1 2 3 4 5 6 8 9 10 11

4 4 4 4 4 3 4 3 4 4

4 4 4 4 4 2 2 1 4 4

4 4 4 4 4 2 1 1 4 4

4 4 4 4 4 1 1 1 4 4

Example 3

In the pad brick test method (according to TGL 14140/01 or 02, wood preservative testing, testing against wood-destroying Basidiomycetes or Moderfauleerreger) inventive formulations of Example 2 are tested. The results are shown in tabular form.

Basidiomyceten recipe from Example 2

Limit values in g Total active substance / m ² Wood Comophora puteana Leutinus lepideus mBoB

M. B.

Androdia stnuosa o.B.

M. B.

Moderfauleerreger

5.5 4.7 3.8 3.8 3.9

Limit values in g total active ingredients / m ² wood

Chaetomium globosum Paecilomyces spec.

m. B. o. B. m. B.

Ceratocystis spec. if.

1.5 1.7 1.5 1.6 1.7

M. B.

1.3

1.5 1.7

1.4

1.8

m B = with UV and water pollution

1.4 1.6 1.7 1.6 1.8

Example 4

In the blue test method (according to TGL 14140/03, wood preservative testing, testing against holzverfarbende fungi) formulations of the invention and Vergleichspraparate tested. The results are given in tabular form.

Test fungus: Pullularia pullulans

Necessary concentration of total active substance for sufficient blue protection in% at 100 g / m ^{2 of} coating material without loading under load

Comparative Examples TBTOinHalbol / Petrol PCP in Half Oil / Petrol DCFinHalbol / Petrol Thiuram in Halol / Xylene Paints according to the invention

1.0 3.2 0.4 1.0

Necessary concentration of total active substance for sufficient protection against blueing in% at 100 g / m ^{2 of} coating material without loading under load

Example 2

Recipe 1.0 1.5

Example 2

Recipe 2 1,1 1,3

Example 2

Recipe 5 1,2 2,2

Example 2

Recipe 10 1.3 2.1

Example 2

Recipe 11 1,2 3,0

Claims (3)

1. Wood-protective coatings based on known binders, fungicidal substances, pigments and excipients, characterized in that they contain a combination of active ingredients from at least two of the classes of compounds tributyltin compounds, tributyltin diaikyldithiocarbamates and Tetraalkylthiuramdisulfide. 2. wood-protective paints according to claim 1, characterized in that 0.1 to 3%, preferably 0.5 to 2% tributyltin compounds and / or 0.01 to 3%, preferably 0.05 to 2% Tributylzinndialkyldithiocarbamate and / or 0, 01 to 3 ° / _{O /} preferably 0.2 to 1.5% Tetraalkylthiuramdisulfide are included. 3. wood-protective paints according to claim 1 or 2, characterized in that the tributyltin compounds, tributyltin oxide, Tributylzinncarboxylate or Tributylzinnsulfid are.