DE4122654A1 - Microbicidal compsns. for protection of technical materials including wood - contain synergistic mixt. of phenolic cpd. and pyrithione deriv, - Google Patents

Abstract

Microbicidal compsn. comprises at least phenolic active agent (I) and at least on pyrithione deriv. (II). (B) active agent compsn. comprises 2-phenylphenol (Ia) and/or a metal salt of (Ia), and 2-mercapto-pyridine-1-oxide (IIa) as the Na and/or Zn salt. Pref. the compsn. (A) the phenolic active agent is (Ia), 4-chloro-3-methylphenol and/or 2-benzyl-4-chlorophenol and/or metal salts of these. The other agent is (IIa) or 2-hydroxy-pyridine-1-oxide and/or the Na and/or Zn salts of these. The compsn. (A) also contains diluents and/or binders or fixers, and opt. siccatives, UV-stabilisers, colours, pigments, process additives, fungicides, and insecticides. USE/ADVANTAGE - Used in protection of wood (claimed). The use of compsn. (B) in protection of technical materials in general (e.g. paper prodn) is also claimed. The compsns. of cut wood. The active agents set synergistically and are ecologically favourable over highly halogenated cpds. The compsns. may also contain insecticidal cpds.

Description

The present invention relates to new microbicidal, synergistic combinations of active ingredients from known Phenol and pyrithione derivatives.

It is known that phenolic active ingredients such. B. 2- Phenylphenol, 4-chloro-3-methylphenol, 2-benzyl-4-chloro phenol, pentachlorophenol and tribromophenol both as such as well as in the form of their metal salts, application as microbicidal active ingredients in the field of material protection Find.

Compared to the toxicological / ecotoxicological questionable highly halogenated phenols z. B. 2- Phenylphenol a halogen-free alternative. For be certain applications is the antimicrobial effectiveness this compound in comparison with the highly halogenated Phenols, however, too low.

The object of the invention is therefore to find toxi ecologically / ecotoxicologically harmless active ingredients  or drug combinations that are currently used Phenols in their action and / or their spectrum of action surpass.

It is also known that pyrithione derivatives such. B. Alkali, aluminum, zinc, tin and bismuth salts of 2-mercapto-pyridine-1-oxide or 2-hydroxy-pyridine-1- oxides antibacterial and fungicidal effectiveness sen (SU Patent -0 98 086, CH-0 05 112, US-5 06 765, US-5 96 801, CA-2 31 576).

A combination of 4-chloro-3-methyl-phenol and salts of 2-mercapto-pyridine-1-oxide is used as a combination of active ingredients nation for stall disinfectants (DE-A-6 36 541).

Furthermore, a mixture of 2-cyclohexylphenols and the zinc salt of 2-mercapto-pyridine-1-oxide as antimicrobial combination of active ingredients in pharmaceutical Preparations described (US-0 79 028).

It has now been found that an active ingredient combination from at least one phenolic active ingredient and min At least one pyrithione derivative has a particularly high micro bicidal, especially fungicidal activity for the protection of Wood.

Surprisingly, the microbicide, in particular the fungicidal activity of the invention Active ingredient combinations significantly higher than the total the effects of the individual active ingredients. So it is  a real synergistic effect. The active ingredient combinations represent a valuable asset to the Technology.

The phenolic active ingredients are in free form or preferably in the form of their metal salts. Preferred phenolic active ingredients are exemplary and preferred as 4-chloro-3-methylphenol, 2-benzyl-4-chlorophenol and especially 2-phenylphenol.

The pyrithione derivatives are preferably in the form of their Metal salts such as alkali, aluminum, tin and bismuth Salts. The sodium, Potassium and zinc salts.

Preferred pyrithione derivatives are 2-hydroxy and ins special 2-mercaptopyridine-1-oxides.

The new combinations of 2- Phenylphenol, or its metal salts, with the Na salt and / or the zinc salt of 2-mercaptopyridine-1-oxide.

The weight ratios of the active ingredients in the active ingredient fabric combinations can be used in relatively large areas can be varied.

The mixtures contain the phenol component in quantities from 0.1 to 99.9% by weight. The rest is 100% by weight Pyrithione component.  

The mixing ratio of phenol component to pyrithione component is preferably 1: 9 to 9: 1, especially preferably 2.5: 7.5 to 7.5: 2.5 parts by weight.

The active substance combinations according to the invention are used to protect industrial materials, since they have a strong action against microorganisms, in particular wood-destroying microorganisms. They are particularly effective against mold, wood-staining and wood-destroying fungi. The following groups of microorganisms may be mentioned by way of example, but without limitation:
Wood-discoloring fungi such as Ascomycetes: Ceratocystis such as Ceratocystis minor;
Deuteromycetes: Aspergillus like Aspergillus niger,
Aureobasidium such as Aureobasidium pullulans, Dactyleum such as Dactyleum fusarioides, Penicillium such as Penicillium brevicaule or Penicillium variabile, Sclerophoma such as Sclerophoma pithyophila, Scopularia such as Scopularia phycomyces, Trichoderma such as Trichoderma viride or Trichoderma viride;
Zygomycetes: Mucor like Mucor spinorus;
Wood-destroying mushrooms like Ascomycetes: Chaetomium like Chaetomium globosum or Chaetomium alba-arenulum, Humicola like Humicola grisea, Petriella like Petriella setifera, Trichurus like Tri churus spiralis;
Basidiomycetes: Coniophora like Coniophora puteana, Coriolus like Coriolus versicolor, Donkioporia like Donkioporia expansa, Glenospora like Glenospora graphii, Gloeophyllum like Gloeophyllum abietinum or Gloeophyl lum adoratum or Gl. protactum or Gloeophyllum sepiarium or Eq. trabeum, Lentinus such as Lentinus cyathiformes or Lentinus edodes or Lentinus lepi deus or Lentinus grinus or L. squarrolosus, Paxillus such as Paxillus panuoides, Pleurotus such as Pleurotis ostrea tus, Poria such as Poria monticola or Poria vapillantia or Poria vapilla placenta or Poria vapia placenta or Poria himantoides or Serpula lacrymans, Stereum such as Stereum hirsutum, Tyromyces such as Tyromyces palustris; Deuteromycetes: Alternaria like Alternaria tenius, Cladosporium like Cladosporium herbarum.

The temporary protection of Lumber.

The amount of active ingredient combinations used is on the type and occurrence of the microorganisms of the Germ count and depending on the medium. The optimal one Set amount can be tested by application rows can be determined. In general, however, it is sufficient 0.001 to 10% by weight, preferably 3 to 9 % By weight of the active ingredient mixtures, based on the protective material.

As such, the new active ingredient combinations can be used in Form of concentrates or general form  such as powders, granules, solutions, suspensions, Emulsions or pastes can be applied.

The formulations mentioned are known per se Made way, e.g. B. by mixing the active ingredients with an extender that consists of liquid solvents or Diluents and / or solid carriers stands, and / or binding or fixing agents, given if siccatives and UV stabilizers and if necessary Dyes and pigments and other processing tools such as B. emulsifiers and dispersants.

Liquid solvents for the active ingredients are included for example water, alcohols, such as lower aliphatic Alcohols, preferably methanol, ethanol, isopropanol and benzyl alcohol; Ketones such as acetone and methyl ethyl ketone; liquid hydrocarbons such as gasoline fractions onen; halogenated hydrocarbons, such as 1,2-dichloro ethane.

The active ingredient combinations can also in aqueous Alkali are dissolved, optionally also in a mixture with water-miscible organic solvents such as e.g. B. methanol or ethanol.

The active substance combinations according to the invention, the agents, concentrates or formulations which can be prepared therefrom can also be used for other z. B. fungicidal active substances or other active substances to enlarge the active spectrum or to achieve special effects are added. In particular, insecticidal active ingredients are used as mixing partners. Particularly favorable Mi partners are z. B. the following connections:
Sulphenamides such as dichlofluanid (Euparen) and methylene euparen, aphthenat organic tin compounds such as Tributylzinnn and tributyltin oxide, carbamates as Carbenda zin and Benzomyl, thiocyanates thiocyanomethylthio benzothiazole (TCMTB), quaternary ammonium compounds such as benzyl dimethyl tetradecylammoniumchlorid and benzyl-dimethyl-dodecylammonium chloride, morpholine derivatives such as C _11, such as - C ₁₄ -4-alkyl-2,6-dimethylmorpholine homologue (tride morph) or (±) -cis-4- [3-tert-butylphenyl) -2-methyl propyl] -2,6-dimethylmorpholine (fenpropimorph) and to organic Wood protection fungicides, and a suitable insecticide such as O, O-diethyl-thiophosphonyl-O-α-acyano benzaldoxime (phoxime), O, O-diethyl-O-3,5,6-trichloro-2-pyridyl-thiophosphate (chloropyriphos) or from the pyrethroid series [5-benzyl-3-furylmethyl-3- (2-methoxycarbonyl-1-propenyl) -2,2-dimethylcyclopropane-carboxylate] (permethrin), [α-cyano-3-phenoxybenzyl-d, k-cis-3- (2,2-dibromovinyl) -2,2-dimethyl-cyclopropane-carboxylate] (decamethrin), [α-cyano-3- phenoxybenzyl (±) cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate] (cypermethrin), [(RS) -α-cyano-3-phenoxybenzyl (R, S) -2- (4-chlorophenyl) -3-methylbutyrate] (fenvalerate), [cyano- (4-fluoro-3-phenoxyphenyl) methyl-3- (2,2-dichloroethenyl) -2,2-dimethyl-cyclopropanecarboxylate] (cyfluthrin) , 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imide azole-2-amine (imidacloprid).

Due to the insecticidal component, effectiveness is achieved not only against the aforementioned fungi but also against wood-destroying insects. Examples - without limitation - are wood-destroying insects:
Hymenoptera such as Sirex juvencus, Urocerus augur, Urocerus gigas, Urucerus gigas taignus, beetles such as Anobium puncta tum, Apate monachus, Bostrychus capucins, Chlorophores pilosus, Dendrobium pertinex, Dinoderus minutus, Erno bius mollis, Heterobususicanus, Heterobususicanus, Heterobususylusus brunneus, Lyctus linearis, Lyctus planicollis, Lyctus pubescens, Minthea rugicollis, Priobium carpini, Ptilinus pecticornis, Sinoxylon spec., Trogoxylon aequale, Trypto dendron spec., Xestobium rufovillosum, Xyleborus spec .; Termites such as Coptotermes formosanus, Cryptotermes brevis, Heterotermes indicola, Kalotermes flavicollis, Mastotermes darwiniensis, Reticulitermes flavipes, Reticulitermes lucifugus, Reticulitermes santonensis, Zootermopsis nevadensis.

The agents or concentrates contain the Invention active ingredient combinations in an amount of 0.01 up to 95% by weight, in particular 0.01 to 30% by weight, in addition optionally 0.001 to 10 wt .-% of a suitable another fungicide, insecticide or another Active ingredient as mentioned above, and 5 to 99% by weight, preferably more than 30% by weight of a mixture Extender and / or binding agent or fixative, added if necessary, siccatives and UV stabilizers otherwise dyes and pigments and other processing training aids.  

Large tech African impregnation processes, as well as by impregnation in plunge pools, spraying or painting the wood with the active ingredient solution or suspension or emulsion aims. For wood secondary products e.g. B. woodcut, cell fabric or intermediates in papermaking the application must be adapted to the technical possibilities fit.

The insecticidal active ingredient component can also be in one applied upstream or downstream process step will.

The active substance combinations according to the invention enable advantageously, the previously available mirkobi to replace ziden means with more effective ones. they show good stability and advantageously have one wide range of effects.

The following examples serve to explain the Invention but not limited to:  

example 1

• 1. Synergistic mixture of fungicides from 2-phenylphenol (B) and 2-mercapto-pyridine-1-oxide, Zn salt (A) 30 parts by weight of 2-phenylphenol and 70 parts by weight of 2- Mercapto-pyridine-1-oxide-Zn salt are used as a solid substances intimately mixed or in a suitable Grind the grinder together. The result is the syner mixture of fungicides as a white powder. Analogously, mixtures of the other Mixing Ver ratios of the components are manufactured. A solution in aqueous alkali can also be used be put.
• 2. Synergistic effectiveness of the invention Active ingredients against wood fungi. The synergistic effectiveness of the fiction moderate active ingredient mixtures can be compared the MIC (minimum inhibitory concentration) values of the pure active ingredients with which the mixtures are made.

Determination of the MIC values

To demonstrate the effectiveness against fungi, the minimal inhibitory concentrations (MIC) in accordance with the invention moderate mixtures determined:  

An agar made from wort and peptone is, with active ingredients according to the invention in Concentrations from 0.1 mg / l to 5000 ml / l ver puts. After the agar solidifies, Kontamina occurs tion with pure cultures of those listed in the table carried test organisms. After 2 weeks of storage at 28 ° C and 60 to 70% rel, air humidity the MIC determines. MIC is the lowest concentration tion of active ingredient, in which no growth through the type of microbe used; she is in the Table 1 below.

According to the method used by Kull et al. (F.C. Kull, P.C. Eismann, H.D. Sylvestrowicz, R.L. Mayer, Applied Microbiol. 9, 538 to 541, 1961) then the synergism is determined. Thereby apply following names:

X = 1 means additivity X <1 means antagonism X <1 means synergism

Q _a = concentration of substance A, which is the MIC
Q _b = concentration of substance B, which is the MIC
Q _A = amount of substance A in the concentration of A / B that inhibits microbial growth
Q _B = amount of substance B in the concentration of A / B that inhibits microbial growth.

The result is shown in Table 2 below ten.  

Table 1

MIC values

Table 2

Example 2

• 1. Synergistic mixture of fungicides consisting of 2-phenylphenol (B) and 2-mercaptopyridine-1-oxide, Na salt (C)
  Analogously to Example 1, the individual active ingredients can be mixed as a solid or alkaline solution.
• 2. Synergistic effectiveness of the fungicide mixture
  Analogous to Example 1, MIC values (Table 3) and the factors X according to Kull et al. (Table 4) determined.

Table 3

MIC values

Table 4

Claims (10)

1. Containing microbicidal agents for protecting wood an active ingredient combination of at least one phenolic active ingredient and at least one pyri thion derivative. 2. Composition according to claim 1, containing as phenolic Active ingredient 4-chloro-3-methylphenol, 2-benzyl-4-chlorine phenol and / or 2-phenylphenyl and / or their Me tall salts. 3. Composition according to claim 1, containing as pyrithione Derivative 2-hydroxy-pyridine-1-oxide, 2-mercapto-pyri din-1-oxide and / or their metal salts. 4. Composition according to claim 1, containing 2-phenylphenol and / or its metal salts and the Na and / or Zn salt of 2-mercapto-pyridine-1-oxide. 5. Composition according to claim 1 containing in addition to the Active ingredient combination according to claim 1, extender and / or binding or fixing agents, if appropriate Desiccants, UV stabilizers, dyes, pigments, Processing aids, other fungicides and Insecticides. 6. Active ingredient combination of 2-phenylphenol and / or its metal salts and the Na and / or Zn salt of 2-mercapto-pyridine-1-oxide.   7. Use of the active ingredient combination according to claim 6 as microbicides to protect technical materials lien. 8. Use of the active ingredient combination according to claim 1 and 6 for the protection of wood against microbial waste construction. 9. Procedure for combating wood-destroying Mi kroben, characterized in that an effect Combination of substances according to claim 1 on the microbes or let their habitat take effect. 10. Process for the preparation of microbicidal agents, characterized in that an active ingredient com combination according to claim 6 with extenders and / or processing aids mixed.