DD155001A1 - WOOD PROTECTIVE PAINTINGS - Google Patents

Abstract

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

Description

22 566

CKEMIEKQMBINAI BITTERFELD. Bitterfeld, November 26, 1980

2071

Wood preserving paints

Field of application of the invention

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

Characteristic "of the known technical solutions

Me coating of paints with active ingredients, which have predominantly fungicidal activity, has acquired technical importance only in recent years, after it has been recognized that biological damage factors to the premature destruction of exterior coatings on organic paint substrates, especially

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Wood, substantially involved »The experience gained in the meantime shows that the known technical solutions, especially with regard to the spectrum of efficacy, effectiveness and toxicological properties, do not meet all the requirements of the conditions of use« Pure wood and other paint coatings containing micro-organisms. find as organic fungicides pentachlorophenol, organic copper compounds, Tributylsinnverbindungen. and increasingly also dichlorofluidide (1-dimethylamino-H-phenyl-H '- (dichlorofluoromethylmercapto) -sulfanide) Use * Pentachlorophenol must be used in high concentrations, does not have sufficient UV stability and is due to possible highly toxic contaminants and its slow degradation to be regarded as an environmental toxin "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 Bestanaigke.it, resulting in the reduction of the economy 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. , '

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Although Dichlofluanid "has a good effect against wood-staining fungi, but is not stable to hydrolysis in the aqueous medium, not UV-stable and must be used because of the low V / effect against Basidiomyceten and moder moderators in high concentrations, resulting in the reduction of the economy.

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-discoloring fungi at low drug concentrations, which usually seek the known technical solutions, whereby the stability of the organic carrier wood or cellulose is initially not affected, but the adhesion and durability of the This reduces the film's peeling and shrinkage of moisture results in shrinkage cracks in the wood, which form a point of attack for wood-destroying fungi. In the modern wood stains, this phenomenon is even more critical to evaluate, because due to the lower binder and pigment content, the UV exposure increases. "The thin film, which is partially permeable to water, but just the main advantage over conventional paints, because only avoiding the film peeling off and extensive preparatory work on indispensable branding paints «

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The object of the invention is the production of paints based on active ingredient combinations with UV stability significantly improved overall protection of wood preserving paints against the totality of wood-damaging fungi with low drug use, reduced harmful load, high efficiency and improvement cause the technical painting properties.

Explanation of the nature of the invention:

The technical task was to develop wood preserving paints or primers that increase the durability of the paint film at low agent concentrations and, until renewal, protect the underlying materials, especially wood and wood materials, from damage from biological attack and weathering Ensure wooden surface.

It has now been found that, surprisingly, tetraalkylthiuram disulfides, in particular tetramethylthiuram disulfide (thiuram), which are useful as rubber additives, less toxic plant fungicides with very short waiting time and fungicide for the preservation of various organic materials, but which are likely to protect wood and wood materials UV-instability found no use, unfolded in inventive combination with tributyltin compounds in paints an excellent effect especially on the surface of wood and wood-based materials en. This may lead to a reaction between the active ingredients to Tributylzinndialkyldithiocärbamaten so that the inventive

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Combinations of 2 to 3 active ingredients exist. 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 substances, it is thus possible to produce coatings containing active substances 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 films represent 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, in combinations of 0.1 % Tributylainnverbindungen with 0.01% Iributylsimidialkyldithiocarbamaten and / or 0.01 % Tetraalkylthiuramdisulfid, in particular Tetramethylthiuramdisulfid comes into question.

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As Tributylzirinverbindungen are ζ * B. Tributylζinnoxid, Tributylzinncarboxylate all kinds, which may also be polymeric, tributyltin sulfide, tributyltin fluoride suitable as Tributylzinndialkyldithiocarbamate are especially tributyltin dimethyl and diethyldithiocarbamate into consideration and. As Tetraalkylthiuramdisulfide in particular tetramethyl and ethylthiuramdisuifid can be used. ,

As binders for the paints according to the invention, virtually all customary binders · alone or in combinations such as * B * all types of alkyd resins, vinyl resins, chlorinated vinyl resins, especially in combination with linseed oils and alkyd resins, but also especially aqueous dispersion types based on polyvinyl acetate and Polyvinylacrylates are used "The amount of binder depends on the goal 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 Anstrilstoffilmes v / earth additionally additionally corresponding organic and / or inorganic pigments, plasticizer _s water repellents, stabilizers, solvents and diluents 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. Purely practical purposes, taking into account the duration of action, are concentrations from 0.1 to. 3, preferably 0.5 to 2 % Tributylsinnverbindungen with. 0.01 to 3, preferably 0.05 to 2 % Tributylzinndialkyldithiooarbamaten and / or 0.01 to 3 _S preference ~: 0.2 to 1 %. Tetraalkylthiuram disulfides used »

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Execution example

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

example 1

Effect of active compound combinations according to the invention in comparison with known solutions against test fungi

.Versuchsbeschreibung:

Schiiffholzpappe in the dimension 4 * 5 x 13 »4 cm is soaked 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 to 26 ⁰ C in the incubator. The evaluation takes place after 10 days.

Boriiturschemas 1 = heavy infestation

2 "average infestation

3 = low infestation

4 a no infestation

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Test fungus Pullularia pullulans

Active substance concentration 0.4 Tributylzinndimethyldithio- 0.1 / 0.3 0.15 / 0.4 UV exposure 100 200 in h 2.0 carbamate / thiuram Tributyltin oxide / tributyltin 0 3 1 300 tributyltin 0.1 / 0.3 diethyldithiocarbamate 4 3 3 1 Pentachlorophenol 0.5 4 4 4 2 Tributyltin oxide / thiuram 4 3 2 4 thiuram 0.2 / 1 4 2 Tributylζinnsaliζylat / 4 4 thiuram 4 4 4 4 4 4 4 4 4 4

Tributylzirmoxid / Tributylzimi & imethyldithiocarbamat /

Thiuram 0.2 / 0.1 / 0.1 4 * 4

Test fungus; Ceratocystis spec.

Tributylζinnoxid / tributyl

tin diethyldithiocarbamate 0.05 / 0.5 tributyltin sulfide / thiuram 0.08 / 0.4

Dichlofluanid 0.8

Tributylzinndimethyldithio-

carbamate / thiuram '0.1 / 0.5 4 4 4 4

Tributyltin oxide / tributyltin ·

dimethyldithiocarbamate 0.05 / 0.3 4 4 4 4

Tributyltin diethyldithiocarbamate / tributyltin sulfide 0.2 / 0.4

Thiuram O ₉ S

Tributyltin oxide 0.6

4 4 4 4 4 4 4 4 4 4 3 2

4 4 4 4 4 2 1 1 4 4 O 1

~

~ 9 -> 225661 2071

Test fungus ι Alternaria humincola active substance. concentration

UV exposure 100 200 in h O 3 2 300 4 4 4 2 4 4 4 4 4 4 4 4 4 4

Tributyltin oxide 0.4

Tributyltin oxide / thiuram 0.2 / 0.5 tributyltin acetate / thiuram 0.1 / 0.3 tributyltin benzoate / thiuram 0.3 / 0.1 tributyltin dimethyidithio

carbamate / TMuram. ^, ^ / 1 4 4 4

Tributyltin oxide / tributyl

tin diethyldithiocarbamate 0.2 / 0.4 4 4 4

Test fungus; Scopularia phycomyces

Thiuram 0.5 4 3 11

Tributyltin diethyldithiocarbamate / Te traäthy1thiuram

disulfide 0.1 / 0.3 4 4 4 4

Tributyltin oxide / Tetra

ethyl thiuram disulfide 0.1 / 0.3 4 4 4 4 pentachlorophenol 5 4 3 3 2

Tributyltin oxide / penta-

Chlorophenol 0.2 / 3 4 4 2 2

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Example 2

Testing of inventive and comparative paints against test fungi

Test Description:

Wood panels are coated on all sides with the paint to be tested, dried and subjected to UV radiation in various doses using the Xenon test. The specimens are then sterilized with propylene oxide. "Sterilized collars are

.... m- ·

Floor introduced, thereafter inoculating with the appropriate spore suspensions _β incubated for 7 days "In this Kolle flasks inserted v / ground small Glasbänkchen at about 22 ⁰ G because, the sterilized test specimens are up down and at 22 ⁰ C 3 to 4 weeks incubated according to the type of mushroom «Afterwards it is rated.

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, Ö

Paraffin 1.

Xylene 40

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2) tributyltin oxide 0.8 Tributylzinndimethyldithiocarbamat 0.2 thiuram 0.2 vinyl resin 15 paraffin 1 silicone oil 1 xylene 81.8

3) tributyltin diethyldithiocarbamate 0.3 thiuram .1.0 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

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9) Thiuram 0.9 polyvinyl acetate 60 water 39.1 10) tributyltin oxide 1 Thiuram 1 chlorinated vinyl resin 5 ' paraffin 2 Iron oxide red VJL 'Xylene 76 alkyd resin 10 11) tributyltin oxide 1 thiuram V chlorinated polyethylene 15 paraffin 1 Iron oxide yellow 5 xylene 72 linseed oil 5

Test fungus j Alternaria humincola recipe

1 2 3 4 5 6 7 8

UV exposure 100 200 in h 0 4 4 300 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 2 2 4 4 3 CV i 1 4 4 3 2 4 3

2 5 6

2071

Test fungus; Scopularia phycomyces

recipe

1 2 3

4 5 6 7

UV exposure 100 200 : in h O 4 4 300 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 CVI 4 4 CVI CVJ 2 4 1

iestpilzi recipe

Pullularia pullulans

UV exposure 100 200 in h 0 4 2 300 4 3 2 1 4 2 CVJ 1 4 4 4 1 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4

6 7 9 1 2 3 4 5 - 14 -

-6

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Test mushroom j recipe

Ceratocyctis spec,

UV exposure 100 200 in h O 4 4 .300 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4. 4 4 4 2 4 4 2 2 2 4 4 2 2 4 4 4 1 4 4

1 2 3 4 5 6 7 8 10

Test fungus: recipe

Alternatives tenuis

UV load in h 0 100 200

1 2 3 4 5 6

7 10 11

4 4 4 4 4 4 4 4 4th 4 4 4 4 , 4 4 4 4 4 4 4 4 3 1 1 4 ' 2 2 1 4 4 · 4 ' 4 4 4 4 4

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- -j 5 22 56 6

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Test fungus: Coniophora puteana

recipe

UV exposure 100 200 in h O 4 4 300 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4th 3 2 4 4 2 2 CVJ 4 4 4 1 4 4 4 4 4 4

1 2 3

io 11

Test fungus: Chaetomium globosum

Recipe UY load in h 0 100 200 300

1 2 3 4 5 6

10

4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 3 CVJ 2 1 4 ' 4 3 1 4 ' 4 4 4

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Test fungus; Androdia sinuosa

recipe

UV load in h 0 100 200 300

3 4 5 6 8 9

   10 11

4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 3 2 CVJ 1 4 2 1 1 3 1 1 1 4 4 4 4 4 4 4 4

Example 3

In the Klötzchentestverfahren (according to TGL 14140/01 or 02, Holzsohutzmittelprüfung, testing against wood-destroying Basidiomycetes or "mildew pathogens) formulations of Example 2 according to the invention are tested.

The results are shown in tabular form.

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Basidiomycetes

Recipe from example 2

Limit values in g total active substance / m

Wood

Cöniophora Leutinus Androdia 'püteana lepideus sinuosa'

M. B. o.B .. m. if. M. B.

10 11

5.5 - 1.4 - 1.5 4.7 1.5 - 1.7 3.8 1.6 - 1.5 3.9 1.7 - 1.6 3.8 1.6 - 1.7

Moder rottener limits in g Total active substance / m wood M. B. if. M. B. Chaetomium glo "bösum Paecilomyces Ceratocystis spec. , spec. 1.2 1.4 M. B. if. 1.7 - '1.6 1 1.3 - 1.4 1.7 2 1.5 - 1.5 1.6 5 1 »7. - 1.7 1.8 10. .1 * 4 mk 11 1.8 -

M. B. s with UV and water pollution

2071

Example 4

In the blue-tint test method (according to TGL 14140/03, wood protection · vibration test, test against wood-discolouring fungi) formulations according to the invention and comparison preparations are tested

 The results are given in tabular form »

Test fungus: Pullülaria pullulans

Comparative preparations TBl ¹ O in half oil / petrol PCP in half oil / petrol DCP in half oil / petrol Thiuram in half oil / xylene

According to the invention e paints

Example 2 Recipe 1

Example 2 Formulation 2

Example 2 Recipe 5

Example recipe

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

1.0 6.5 3.2 10.0 0.4 4.0 1.0 .6.5 1.0 1.5 1.1 1.3 1.2 2.2 1.3 2.1 1.2 3.0

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Claims (6)

-19- 225661 2071 Invention claim 1. wood-protective paints, characterized in that the active ingredients from at least two of the classes of compounds tributyltin compounds, Tributylzinndialkyldithiocarbamate and Tetraalkylthiuramdisulfide included. 2. wood-protective paints according to item 1, characterized in that o, 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 %, preferably 0.2 to 1.5 % Tetraalkylthiuramdisulfide are included. Wood preserving paints according to item 1 or 2, characterized in that the tributyltin compounds are tributyltin oxide, tributyltin carboxylates or tributyltin sulfide. - 20 - -20- 2 2 5 6 6 1 2071 4. Wood-protective paints according to one of the items 1 to 3 »characterized in that they contain as binders alkyd resins, vinyl resins, chlorinated vinyl resins, polyvinyl acetate and / or polyacrylate. 5 "Wood-protective paints according to one of the items 1 to 3", characterized in that they contain as binders vinyl resins and / or chlorinated vinyl resins in combination with drying oils and / or alkyd resins « 6. Wood preservative paints according to one of the items 1 to 3 », characterized in that they 5 to 30 %, preferably 8 to 22 % chlorinated vinyl resins and 2 to 10 % drying oils in combination with 0.1 to 3 $, preferably 0.5 up to 2.5 % paraffin and 0.5 to 4 %, preferably 1 to 2.6 % chlorinated paraffin and pigments for coloring dissolved or suspended in aromatic hydrocarbons «