FI68500B - CONTAINING CONCENTRATED BACTERICIDES AND FUNGICID EFFECTS WITH ANALYSIS OF DETSAMMA - Google Patents

Description

1 68500

Aqueous concentrate that kills bacteria and kills fungi and its use

The invention relates to an aqueous concentrate having a bactericidal and fungicidal action, which is particularly suitable as an aqueous preparation, wood preservative, disinfectant, biocide in paints and bactericidal and fungicidal agent in textiles, plastics, adhesives, building materials. - and cut-10 in moon oils and circulating cooling waters to finish to kill bacteria and kill fungi.

The aqueous concentrate according to the invention is characterized in that it contains a mixture of active ingredients comprising a) emulsified trialkyltin compounds having a total number of C atoms of tin-bonded alkyl groups of 9 to 12, or triphenyltin compounds, with the exception of N, N) and hydrogen halides; -cyclohexyldiacenium oxide alkali salt. The weight ratio of active ingredients in the mixture is preferably 5: 1 to 1: 5, in particular 3: 1 to 1: 3.

The invention also relates to the use of such a concentrate as a wood preservative, wherein the concentrate is in the form of an aqueous preparation containing a conventional emulsifier having an active ingredient concentration of 0.1 to 3% by weight.

The high efficacy of triorganotin compounds against microorganisms such as harmful fungi and bacteria is known. The optimum effect of this class of compounds is generally evident when the total number of C atoms of the tin-bonded alkyl groups is 9-12. Shorter or longer groups attenuate the biocidal effect. The spectrum of action of the triorganotin compounds is relatively broad. However, the activity against various microorganisms, for example gram-negative bacteria and certain bluetongue, is relatively weak.

35 Another group of biocidal products, which are mainly used as wood preservatives, is described in the DE patent.

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2,685,500 in 1,024,743. These are the salts of Ν'-hydroxy-N-alkyl-diazenium oxide. The disadvantage of these compounds is that, in order to protect the wood, the application concentrations must be high and the effect against wood-staining fungi and wood-contaminating bacteria is minimal.

For these reasons, it has been proposed to use mixtures of N'-hydroxy-N-alkyldiazenium oxide salts and other specific biocidal substances in order to moderately enhance the effect or broaden the spectrum of action. (DE application publications 10 2 336 290, 2 341 882).

DE-A-2 633 452 describes triorganotin compounds of hydrodiazenium oxides. These compounds are highly soluble in organic solvents and are particularly suitable for use in oily wood preservatives.

It has now surprisingly been found that mixtures of trialkyltin compounds and salts of N * -hydroxy-N-cyclohexyldiazenium oxide have a synergistic effect, in particular against gram-negative bacteria and fungi, which generally belong to the class of fungi which are difficult to control and Fungi imper-20 fectisia. An improvement in the effect can also be observed against wood-destroying fungi and gram-positive bacteria.

The concentrate according to the invention can be used excellently as an aqueous preparation, in particular as a wood preservative, for example to protect freshly felled wood which is easily exposed to bacteria and fungi such as Aspergillus and Trichoderma species; as well as for the protection of building timber, whereby the synergistic effect of the active compound combination according to the invention provides protection against wood-polluting fungi and also against bacterial pests. Bacteria do not cause wood to decompose, but can nonetheless contribute to the detrimental effect of fungi.

For the preparation of aqueous preparations, conventional emulsifiers, preferably nonionic emulsifiers such as alkylaryl polyglycol ethers, can be added to the concentrate according to the invention. In such concentrates, the concentration of the active ingredient mixture is 10-25% by weight; these can be easily diluted to stable use concentrations.

The concentrate according to the invention is also suitable for use as a biocide in aqueous coating systems, for example in dispersions, as a potter against the spoilage action of bacteria and fungi, in particular also against bleaching of aqueous wood brush systems, for example alkyd resin dispersions.

10 Similarly, aqueous preparations can be used as biocides to protect various materials such as papers, cardboard, plastics, textiles, adhesives, building materials and leather.

An additional field of application is the protection of aqueous solutions, such as circulating cooling waters, papermaking waters or drilling and cutting oils, against unwanted and Mirko organisms.

The active substance concentrations are, depending on the area of application, 0.1-5% for wood protection, 0.05-3% for the protection of brush systems, papers, textiles, building materials, etc., and 0.0001-0.2% for cooling and industrial waters and drilling. - and for the protection of cutting oils.

Example 1 Preparation containing 10% of active ingredient 25 parts by weight of tri-n-butyltin oxide 20 "30% aqueous solution of the potassium salt of N'-hydroxy-N-cyclohexyldiazenium oxide 20" non-ionic emulsifier (Marlowet 30 ISM) 56 "water

The ingredients are homogenized by mixing to give a clear - very slightly turbid mixture which, when diluted with tap water in a ratio of up to about 1:50, gives 35 stable, clear - slightly opalescent preparations.

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4,685,500

Example 2 Preparation containing 10% of active ingredient 5.7 parts by weight of tri-n-butyltin oleate 14.3 "of 30% aqueous solution of the potassium salt of N'-hydroxy-N-cyclohexyldiacenium oxide 21.5" non-ionic emulsifier (Marlowet ISM) 58.5 "water 10 The ingredients are homogenized by mixing to give a clear - very turbid mixture which, when diluted with tap water in a ratio of up to about 1:50, gives stable, clear - up to opalescent preparations. Example 3 15% active ingredient preparation 12 parts by weight of tri-n- butyltin naphthenate 40 "30% aqueous solution of the potassium salt of N'-hydroxy-N-cyclohexyldiazenium oxide 20 48" non-ionic emulsifier (Marlowet ISM)

The ingredients are homogenized by mixing to give a clear - quite turbid mixture, which, when diluted with tap water in a ratio of up to 1: 100, gives sta-25 bile, clear - slightly opalescent preparations. Example 4 Preparation containing 15% of active ingredient 6 parts by weight of tri-n-butyltin abiethate 30 "30% aqueous solution of the potassium salt of N-hydroxy-N-cyclohexyldiacenium oxide 24" non-ionic emulsifier (Marlowet ISM) 40 "water 35 Ingredients homogenize by stirring to obtain a clear - very slightly turbid mixture, which, when diluted with tap water with a maximum ratio of 1:75, gives stable, clear - slightly opalescent preparations.

table 1

To compare the effect, round paper filters (φ5.5 cm) moistened with aqueous solutions further moistened with ni-5 were air-dried and then placed in Petri dishes on Plate-Count-Agar inoculated with a bacterial suspension and incubated for 2 days +37 ° C. The sizes of the inhibitors around the filter were then determined:

Blocking areas, e.g.

Active ingredient solution Weight% Bacillus Bacillus Proteus _subtilis mesentericus vulgaris tri-n-butyltin- 1 12-15 12-15 5-7 15 oxide 0.5 10-12 12-15 3-5 0.2 10-12 10-12 0 -1 tri-n-butyltin-1 6-7 7-8 2-3 linoleate 0.5 4-6 5-6 1-2 0.2 2-3 3-4 0-1 20 N-hydroxy-N- potassium salt of cyclo 1 0-1 2-4 0 hexyldiazenium 0,5 0 0-1 0 oxide 0,2 0 0-1 0

Example 1 1> 15> 15 12-15 0.5> 15> 15 8-10 25 0.2 10-12> 15 6-8

Example 2 1 12-15 12-15 12-15 0.5 10-12 10-12 12-15 0.2 9-10 10-12 8-10

Table 2 30 Round paper filters moistened according to the method of Table 1 were placed on biomass agar sprayed with a spore suspension of test fungi and incubated for 3 weeks at 230 ° C. Inhibition zones around the samples were then determined.

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Blocking areas, nun

Active ingredient- Weight% Trichoderma Cladosporum Aspergillus Pullularia solution_viride _herfarum versicolor pullulans tri-n-butyl- 1.0 4-6 6-8 6-8 2-3 5 tin oxide 0.5 3-5 2-4 3-4 1- 2 0.2 2-3 0-1 1-2 0-1 tri-n-butyl-1.0 2-3 2-3 3-4 1-2 naphthenate 0.5 1-2 1-2 1-2 0-1 0.2 0-1 0 0 0 10 tri-n-butyl-1,0 2-3 1-2 2-3 1-2 tin abietate 0.5 1-2 0-1 0-1 0 -1 0.2 0-1 0 0 0 N-hydroxy-N- 1,0 0X 5-7 2-4 4-8 cyclohexyldi- 0,5 0X 0 0X 0 15 potassium salt of azinium oxide 0,2 0X 0 0X 0

Example 1 1 8-10 12-15> 15 12-15 0.5 5-7 10-12 12-15 10-12 0.2 2-3 8-10 10-12 10-12 20 Example 3 1 5- 6 10-12 12-15 10-12 0.5 3-4 8-10 10-12 10-12 0.2 1-2 6-8 8-10 8-10

Example 4 1 4-5 10-12 12-15 10-12 0.5 3-4 6-7 9-10 8-10 25 0.2 2-3 4-5 6-8 6-8 x) The strength of the sample growth

Table 3

According to the method of Table 2, the inhibition areas around the samples were determined: ^ Inhibition areas, e.g.

Active ingredient solution Weight% Chaetomium Poria Lenzitis _globosum monticula tabea_ tri-n-butyl- 0.5 8-10 7-9 10-12 35 tin oxide 0.2 6-8 5-7 6-8 7 08500

Blocking areas, nun

Active ingredient solution Weight% Chaetomium Poria Lenzitis _globosum monticula Tabea tri-n-butyltin- 0.5 3-4 3-4 5-7 5 linoleate 0.2 1-2 1-2 2-3 tri-n-butyltin- 0, 5 2-3 2-3 4-5 naphthenate 0.2 0-1 1-2 2-3 Ν'-hydroxy-N-0.5 2-3 4-6 4-5 cyclohexyldi- 0.2 0 0 0 10 Potassium salt of azinium oxide

Example 1 0.5 12-15 8-10 12-15 0, 8-10 6-8 8-10

Example 2 0.2 3-4 3-4 4-6 15 Example 3 0.5 5-7 4-5 6-8 0.2 2-3 3-4 4-5

For comparison, pine surface wood pieces measuring 5 x 2.5 x 1.5 cm were soaked in the following aqueous solutions of the active ingredients: 20 A 2% tri-n-butyltin naphthenate B 2% potassium salt of N'-hydroxy-N-cyclohexyldiacenium oxide C 2% active compound combination of Example 3 no active substance 25 After drying and sterilization, each active and non-active wood piece was placed in a Kolle dish with Biomalz agar sprayed with spore suspensions of test fungi and incubated for 10 weeks at + 30 ° C: in. The growth of the fungal mycelium in the samples or samples was then visually assessed: - I! 8 68500

The test fungi

Wetting of the active ingredient Trichodem viride Pullularia pullulans solution Absorption Sample Sample

Weight% growth * HZX growth * HZ * 5 A 0.031 - 1-2 D - +++ 0 A 0.033 - 0-1 D - +++ - B 0.034 ++ 0 10 D - + + + 0 B 0.030 - 1-2 D - +++ 0 C 0,029 - 4-5 D - +++ 0 15 C 0,033 - 3-4 D - + + + 0 x) Sample growth: = no growth + = slight growth 20 ++ = medium growth +++ = strong growth HZ = inhibition area around the sample, e.g.

Claims (3)

9 68500 An aqueous concentrate having bactericidal and fungicidal activity, characterized in that it contains a mixture of active ingredients comprising a) emulsified trialkyltin compounds having a total number of C atoms of tin-linked alkyl groups of 9 to 12, or triphenyltin compounds, with the exception of triorgano halogen , and b) an alkali salt of N1-hydroxy-N-cyclohexyl-diacenium oxide. Concentrate according to Claim 1, characterized in that the weight ratio of the action zones in the mixture is from 5: 1 to 1: 5, in particular from 3: 1 to 1: 3. Use of a concentrate according to claim 1 or 2 as a wood preservative, wherein the concentrate is in the form of an aqueous preparation containing a conventional emulsifier having an active ingredient concentration of 0.1 to 3% by weight.