FI56500C - TRAEBIOCID PAO BASIS AV EN TRIALKYL- ELLER TRIARYLTENNFOERENING TILL FRAMSTAELLNING AV TRAESKYDDSMEDEL - Google Patents

Description

Γο1 .... KU RELEASE - _ _ Α Λ Β 11 UTL AGG N I N G SSKRI FT 56500 ^ ^ ^ (51) Kv.ik ^ intfci. ' ΪΒ έ7 ~ κ 3/50 σ 09 D 5/14 A 01 Ν 9/02 FINLAND — FINLAND (*) Patent application - PatcnMnsBhnlng 7 51179 (22) Hakemlsplivl - Ansöknlngsdag 21.0U.75 (23) Initial number - Giltlghetsdig 21.0U.75 (41) Became Public - Bllvlt offentllg 27.10.75

Patent and Registration Office .... ... , . , 1 (44) NlhtlvSksIpanon Ja kuul.Julkalsun pvm. -

Patent-och registerstyrelsen 'Anaökan utlagd oeh utl. «Krlft« n publlcerad 31.10.79

(32) (33) (31) Privilege claimed — Begird prlorltet 26.OU.7U

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 21 + 20235-5 - (71) Hiedel - de Haen Aktiengesellschaft, 3016 Seelze, Federal Republic of Germany - Förbundsrepubliken Tyskland (DE) (72) Hans Schmitt, Gehrden, Gugarbz, Eugen Scholz Paul Brettner, Seelze,

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) (7U) Oy Kolster Ab (5U) Wood biocide based on a trialkyl or triaryltin compound for use in the manufacture of wood preservatives - Träbiocid pä basis a · ^ en trialkyl- eller triaryltennförening account

The invention relates to a wood biocide based on a trialkyl or triaryltin compound for use in the manufacture of wood preservatives. Wood preservatives are substances used to protect wood and wood materials against the destructive effects of fungi and insects.

It is known that organotin compounds, such as tributyltin oxide or triphenyltin acetate, have fungicidal properties. Chlorinated hydrocarbons such as dichlorophenyltrichloroethane, hexachlorocyclohexane or enodosulfan have a good insecticidal effect, but no or very unsatisfactory fungicidal effect.

It was now found that the antifungal effect of organotin compounds cannot be significantly increased when used in combination with endosulfan. The effect of the mixture according to the invention on wood-staining or wood-damaging fungi is substantially greater than that of the organotin compound alone, although the second component of the alloy, endosulfan alone, has no effect on fungal growth. This improved potency of organotin compounds is thought to be due to the synergism of both active ingredients.

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The wood biocide according to the invention is characterized in that it contains (a) endosulfan (N, N, N-hexachlorobicyclo-2,2,1) -heptene- (2-b) oxymethylene- (5,6) -sulfite , and (b) tributyltin oxide, tributyltin fluoride or triphenyltin acetate, wherein the weight ratio of a) and b) of the mixture is 1: 5 to 20: 1, preferably 1: 1 to U: 1.

The fungicidal properties of the active ingredients are studied in nutrient media. The media are incremented and infested with test fungi (Ascomycetes and Basidiomycetes) and incubated. Additions that completely inhibit the growth of test fungi are the minimum inhibitor concentrations (MHK values). The following table contains these values as a percentage of the total: 1_2_3 H_§_6 7 8

Tributyltin oxide (TBTO) 0.005 0.002 0.002 0.002 0.001 0.005 0.001 0.005

Triphenyltin acetate (TPTA) 0.03 0.01 0.03 0.1 0.01> 1 0.1 0.1

Endosulfan> 1> 1 ^ ^ ^ ^ ^ (ES)

Mixture: 1 part ΤΒΤ0 + 1 part ES 0.0005 0.001 0.0005 0.0005 0.001 0.0005 0.001

Mixture: 1 part TPTA + 1 part ES 0.005 0.005 0.001 0.0005 0.005 0.1 0.05 0.05

Mixture: 1 part TBT0 + 1 part ES 0.001 0.001 0.001 0.001 0.001 0.005 0.002 0.002

Mixture: 1 part TPTA + h part ES 0.002 0.005 0.005 0.01 0.01 0.1 0.05 0.05 3 56500

Test fungi: 1. Alternaria consortiale 2. Auriobasidium pullulans Aspergillus niger 4. Penicillium funculosum 5 · Chaetomium globosum (decay fungus) 6. Coniophora puteana (cellar fungus) 7. Lenzites abietina 8. Poria monticola (white pore fungus)

The compounds of the invention have much better MHC values than the individual components used. For example, TBTO has an MHK value of $ 0.005 for Alternaria consortiale *. The 1: 1 MHK value of a mixture of TBT0 with ES in a 1: 1 ratio could be expected to be $ 0.01. However, the actual value is "$ 0.001, which corresponds to an increase in power of $ 100. With an ES: TBTO mixing ratio of 4sl, the MEK should be $ 0.025. However, $ 0.001 was found.

Examination of the mixture according to the invention also in accordance with DIN 52 176 (block test) clearly shows an enhanced increase in effect. In this test, pine wood blocks are impregnated with solutions containing graduated amounts of active ingredient. The blocks are exposed to wood-destroying fungi for 5 months. Power limits are expressed in two numbers. A higher number describes the lowest concentration at which the adverse effect no longer occurs. A lower number indicates the concentration at which wood damage can still be observed:

Table

Coniophora Lentinus Poria puteana lepideus monticola

Tributyltin oxide 0.04-0.1 0.0063-0.016 0.0025-0.0063

Endosulfan ineffective ineffective ineffective

Mixture: 1: 1 0.025-0.04 0.004-0.01 less than 0.001

Mixture: 1: 3 0.04-0.1 0.004-0.01 0.0025-0.0063

Tributyltin fluoride 0.04-0.1 0.001-0.0025 0.0025-0.0063

Mixture 1: 1 0.025-0.04 less than 0.001 0.001-0.0025 4 56S00

No increase in potency was expected, especially since endosulfan clearly has no antifungal effect. However, it does not have much practical significance and offers an opportunity to reduce the use concentrations of organotin compounds. This is essential both for the toxicity of this group of active substances and for their economic aspects.

The longer shelf life achieved by using the substances according to the invention is also essential in practice.

The use of the substance according to the invention can take place in a known manner, for example by mixing it with wood brushes. The simplest way is to dissolve the active ingredient combination in gasoline to a concentration of 0.1-5% and brush the wood parts, or treat them by spraying or dipping. Lubricants having an active ingredient content according to the invention can also be mixed with film-forming agents, synthetic or natural resins, oils or waxes, so that in practice the usual common primers are obtained. Aqueous use is also possible, in which case suitable co-solvents or emulsifiers must be provided to ensure good active ingredient distribution. The active ingredient concentration can vary from 0.1 to one and is selected as required.

Example 1: 20 parts of endosulfan and 10 parts of tributyltin oxide are dissolved in 70 parts of test gasoline. This active ingredient concentrate is used to make finished wood preservatives to kill fungi. The amounts to be added are chosen so that the concentration of active substance is between 0.1 and 5%.

Example 2:

The high boiling gasoline fraction (b.p. 180-200 ° C) is mixed with 0.6 parts by weight of endosulfan, 0.9 parts with triphenyltin acetate and 0.5 part with tributyltin oxide. This mixture is used to brush building wood. Thanks to the high boiling point of the solvent, good penetration and long-term effect are achieved.

Example 5 ♦

To protect fresh lumber, a mixture of 75 parts of butyl glycol, 24 parts of water, 0.5 parts of tributyltin oxide and 0.5 parts of endosulfan is prepared. This mixture protects freshly felled and debarked trees from primary fungal contamination. At the same time, the use of endosulfan has a protective effect against insect contamination.

Example 4:

A solvent-containing wood lubricant has the following composition: tall oil alkyd resin solution 50- $ 50 parts by weight

Glaze pigment 2 "" 5

S 6 SO O

petrol hydrocarbon kp. at about 200 ° C 47 parts by weight of a desiccant 0.2 "" Ketone inhibitor 0.2 "" antifoulant 0.6 "" 5 parts of the active compound concentrate shown in Example 1 are mixed with this wood preservative. This material can be used to brush wooden boards, window frames, doors, etc.

Example 5:

A water-dilutable absorbent primer having the composition: synthetic resin, neutralized, 60% by weight 58 parts by weight butyl glycol 50 "" "water 10" "tributyltin oxide 1" "endosulfan 1" "has a considerable depth effect. against insect damage.

Example 6:

Water-dilutable wood preservative varnish having the following composition: artificial resin, medium-oil, water-dilutable, 20 parts by weight, 75 - by weight iron oxide 2 "" flux 0,5 "" desiccant 0,5 "" _ triethylamine 5,2 ""

isopropyl alcohol 9.0 "M

protection against bluetongue 1.0 "" water 64.0 "" is used for surface protection against fungal and insect contamination.

To this wood preservative varnish is added 1 part by weight of wood preservative biocide comprising 0.6 parts of trihutyltin fluoride and 0.4 parts of endosulfan.