Note: Descriptions are shown in the official language in which they were submitted.
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Synergistic Mixtures
The present invention relates to novel synergistically effective mixtures
comprising, firstly,
triadimefon and/or triadimenol and, secondly, known insecticides, to
compositions based on these
mixtures and to the use of these mixtures and compositions for protecting
industrial materials, in
particular wood and timber products, and also wood/plastic composites, against
attack, damage
and/or destruction by biological pests.
In principle, the person skilled in the art differentiates between structural
destruction of wood by
basidiomycetes and - if the wood is exposed to an environment with high
humidity or soil contact -
by mould fungi, and a damage of the wood by wood-destroying insects and
termites and an optical
impairment of the wood by wood-discolouring fungi. These destructions and
impairments of the
wood lead inter alia to a reduction of strength and in general to a reduced
usefulness of the wood.
As a consequence, wood and timber products are protected with fungicides and,
if appropriate,
insecticides against attack by biological pests, thus prolonging the
usefulness and service life of
wood and timber products.
Triazoles such as, for example, tebuconazole (cf. EP-A 254857) and
cyproconazole (cf. EP-
A 554833) are already known to be useful in the protection of wood against
wood-destroying
basidiomycetes. Their activity in the laboratory test alone is promising;
however, under practical
conditions, a sufficient protection of the wood is not always ensured, so
that, in practical
applications, these active compounds have to be combined with metals or metal
salts, in particular
copper salts. Thus, in practice, triazol fungicides are frequently combined
with heavy metal-
containing compounds, such as, for example, copper compounds, to provide, in
addition to a
fungicidal finish, insecticidal protection.
However, the use of heavy metal-containing compositions for the protection of
wood is to be
considered objectionable for ecological reasons. Accordingly, there was still
a need for improved
compositions for the protection of wood based on active compounds which ensure
a sufficient
protection of wood without the addition of heavy metals.
Triadimefon (( )-1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-triazol-1-
yl)butan-2-one) and
triadimenol (( )-1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-triazol-1-
yl)butan-2-ol) are known
fungicides for the protection of plants against attack by fungi (cf. DE-A
2552967); however, they
cannot be employed on their own in the protection of wood since the activity
spectrum against the
microorganisms relevant in the protection of wood has gaps (cf. EP-A 254857).
An activity against
insects has not been reported.
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Triadimefon or triadimenol are mentioned in some literature references (for
example
WO 00/71314) as possible mixing partners for various active compounds for the
protection of
wood; however, these prior-art mixtures still require improvement in many
respects and, owing to
the activity gaps mentioned above, do hitherto not play any role in the
protection of wood.
Accordingly, there was still a need for an improved active compound mixture
based on triadimefon
and/or triadimenol.
Surprisingly, it has been found that the combination of triadimefon or
triadimenol, which are not
effective on their own, with certain insecticides shows a synergistically
enhanced activity against
biological pests relevant in the protection of wood.
The present invention provides mixtures comprising synergistically effective
amounts of
triadimefon and/or triadimenol and at least one insecticide, preferably from
the group consisting of
phosphoric esters, carbamates, ureas, pyrethroides, pyrroles, phenylpyrazoles,
diphenyl ethers,
diacylhydrazines and nitromethylenes.
The mixtures according to the invention show a synergistic activity against
biological pests
relevant in the protection of wood, i.e. the activity of the synergistic
mixtures is, in an unexpected
manner, higher than the sum of the activities of the active compounds in
question on their own.
Thus, an unforeseeable synergistic effect is present, and not just an addition
of activities.
The present invention furthermore provides the use of the synergistic mixtures
according to the
invention for protecting wood, timber products and wood/plastic composites
against biological
pests relevant in the protection of wood, in particular against wood-
destroying bark beetles and
termites.
The synergistically enhanced activity has the additional advantage that, owing
to the lower amount
of fungicide to be used in a composition for the protection of wood according
to the present
invention, not only an economical advantage is obtained, but the safety risk
to the environment is
also reduced.
Preference is given to mixtures comprising triadimefon and/or triadimenol and
at least one
insecticide from the group consisting of:
acetamiprid, allethrin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin,
bioallethrin, 4-chloro-2-(2-
chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone (CAS-
RN: 120955-
77-3), chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin, cyhalothrin,
cypermethrin, deltamethrin,
etofenprox, fenoxycarb, fipronil, flufenoxuron, hexaflumuron, imidacloprid,
nitenpyram,
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permethrin, pyriproxifen, silafluofen, tebufenozide, thiacloprid,
thiamethoxam, tralomethrin,
triflumuron.
Very preferred are mixtures comprising triadimefon and/or triadimenol and at
least one insecticide
from the group consisting of:
bifenthrin, chlorfenapyr, chlorpyrifos, clothianidin, cyfluthrin,
cypermethrin, deltamethrin,
etofenprox, fipronil, flufenoxuron, imidacloprid, permethrin, thiacloprid,
thiamethoxam.
Especially preferred are mixtures comprising triadimefon and/or triadimenol
and at least one
insecticide from the group consisting of:
bifenthrin, chlorfenapyr, clothianidin, cyfluthrin, cypermethrin,
deltamethrin, imidacloprid,
permethrin, thiacloprid.
The weight ratios of the active compounds in the active compound mixture can
be varied within a
relatively wide range. Preferred are weight ratios of triadimefon and/or
triadimenol to at least one
of the insecticides mentioned in the range from 1000:1 to 1:1, particularly
preferably from 100:1 to
2:1.
Especially preferred are active compound mixtures according to the invention
comprising
triadimefon and/or triadimenol and at least one of the insecticides mentioned
in a weight ratio of
from 50:1 to 5:1.
The synergistic mixtures according to the invention have a particularly high
biocidal, in particular
fungicidal and insecticidal, and also termiticidal action, combined with a
broad activity spectrum
against biological pests which are of relevance in the protection of
materials. They are especially
effective against wood-destroying basidiomycetes and insects, in particular
wood-destroying
beetles and termites.
The following microorganisms may be mentioned by way of example, but not by
way of
limitation:
Chaetomium globosum, Glenospora graphii, Humicola gisea, Petriella setifera,
Trichurus spiralis
and Lecythophora mutabilis, and also against Trichoderma viride, Stachybotrys
cartarum,
Chephalosporium sp. and Acremonium sp.
Coniophora puteana, Coriolus versicolor, Gloeophyllum abietinum, Gloeophyllum
trabeum,
Lentinus tigrinus, Poria monticola, Poria placenta, Serpula lacrymans, Stereum
sanguinolentum,
Tyromyces palustris
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The following wood-destroying insects may be mentioned by way of example, but
not by way of
limitation:
beetles, such as, for example, Hylotrupes bajulus, Chlorophorus pilosis,
Ahobium punctatum,
Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius
mollis, Priobium
carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus
linearis, Lyctus pubescens,
Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec.,
Apate monachus,
Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus
minutus;
hymenopterans, such as, for example, Sirex juvencus, Urocerus gigas, Urocerus
gigas taignus,
Urocerus augur;
termites, such as, for example, Kalotermes flavicollis, Crypotermes brevis,
Heterotermes indicola,
Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucilugus,
Mastotermes
darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Under moist conditions, in addition to mould fungi, bacteria, such as, for
example,
Caldocellulosiruptor sp., Anaerocellum sp., Clostridium species, such as
Clostridium
cellulovorans, Clostridium aldrichii, Cellulomonas species, streptomycetes,
Micromonospora sp.,
Thermomonospora sp., Microbispora sp. and also Cytophaga and Sporocytophaga
species may
also contribute decisively to the degradation of cellulose.
To widen the activity spectrum or to obtain particular effects, the
synergistic mixtures according to
the invention can be combined with at least one further microbicidally active
compound. In
particular, the synergistic mixture may comprise at least one further active
compound from the
group of the fungicides and antibacterially active compounds.
Preference is given in particular to mixtures with one or more of the
following microbicidal
components: dichlofluanid, tolylfluanid, carbendazim, fenpropimorph,
bethoxazin, thiocyanato-
methylthiobenzothiazol, 3-iodo-2-propynyl n-butylcarbamate, zinc pyrithione,
copper pyrithione,
N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine, tebuconazole, propiconazole,
cyproconazole
and copper salts.
Especially preferred are mixtures according to the invention comprising, as
further component,
dichlofluanid, tolylfluanid, bethoxazin, 3-iodo-2-propynyl butylcarbamate,
zinc pyrithione or
copper pyrithione, tebuconazole, propiconazole, cyproconazole, copper salts or
a mixture of these
components.
Preference is also given to mixtures with one or more of the following
bactericidal components:
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benzyl alcohol mono-(poly)-hemiformal, ethylene glycol hemiformal, N-(2-
hydroxypropyl)amino-
methanol, N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3 -one,
4,5-benzisothiazo-
linones, formaldehyde, glutardialdehyde, benzalkonium chloride,
benzyldimethyltetradecylammo-
nium chloride, benzyldimethyldodecylammonium chloride, 3-methyl-4-chlorophenol
and 2-benzyl-
4-chlorophenol and their alkali metal and alkaline earth metal salts, p-
hydroxybenzoic esters, and
also o-phenylphenol and their alkali metal and alkaline earth metal salts,
bronopol, 2,2-dibromo-3-
nitrilepropionamide and silver compounds.
Preference is given to active compound combinations according to the invention
with the
following bactericides:
benzyl alcohol mono-(poly)-hemiformal, N-methylisothiazolin-3-one, 5-chloro-N-
methylisothiazo-
lin-3-one, 4,5-benzisothiazolinones, glutardialdehyde, benzalkonium chloride,
bronopol, 3-methyl-
4-chlorophenol and also 2-benzyl-4-chlorophenol and the alkali metal and
alkaline earth metal
salts, o-phenylphenol and their alkali metal and alkaline earth metal salts,
and silver compounds.
Very particular preference is given to active compound combinations with the
following
bactericides:
benzyl alcohol mono-(poly)-hemiformal, 4,5-benzisothiazolinone, benzalkonium
chloride,
bronopol, 3-methyl-4-chlorophenol and also 2-benzyl-4-chlorophenol and their
sodium and
potassium salts, o-phenylphenol and the sodium and potassium salts, and
silver(I) compounds.
The mixtures according to the invention generally comprise 0.01 - 85 per cent
by weight of triadi-
mefon and/or triadimenol, 0.001 - 15 per cent by weight of at least one of the
insecticides
mentioned and, if appropriate, 0.01 - 80 per cent by weight of at least one
further microbicidally
active compound, in particular from the group of the active compounds
mentioned above.
Preferably, the mixtures according to the invention comprise 0.1 - 40 per cent
by weight of
triadimefon and/or triadimenol, 0.01 - 5 per cent by weight of at least one of
the insecticides
mentioned and, if appropriate, 0.05 - 30 per cent by weight of at least one
further microbicidally
active compound, in particular from the group of the active compounds
mentioned above.
The mixtures according to the invention can be prepared in a known manner, for
example by
grinding and/or mixing and/or granulating the active compounds in a suitable
apparatus. It is also
possible to dissolve, to disperse or to emulsify the active compounds
individually or jointly in a
suitable solvent, if appropriate with addition of further auxiliaries and
additives, such as, for
example, emulsifiers, and, if appropriate, to precipitate them from this
solvent by adding further
solvent or, if appropriate, removing the solvent to dryness by distillation.
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The present invention furthermore provides the use of the active compound
mixtures according to
the invention for protecting industrial materials, in particular wood, timber
products and
wood/plastic composites, against attack, damage and/or destruction by
biological pests, in
particular by fungi and insects.
Depending on their particular physical and/or chemical properties, the active
compounds and the
active compound mixtures can be converted into the customary formulations,
such as solutions,
emulsions, suspensions, powders, foams, pastes, granules, aerosols and
microencapsulations in
polymeric substances.
The present invention furthermore provides microbicidal compositions
comprising a
synergistically effective amount of triadimefon and/or triadimenol and at
least one of the
insecticides mentioned and at least one diluent or solvent, if appropriate
further auxiliaries and
additives and also, if appropriate, at least one of the abovementioned further
active compounds
The formulations can be prepared in a known manner, for example by mixing the
active
compounds with extenders, i.e. liquid solvents, pressurized liquefied gases
and/or solid carriers, if
appropriate with the use of surfactants, i.e. emulsifiers and/or dispersants
and/or foam formers. If
the extender used is water, it is also possible to employ, for example,
organic solvents as auxiliary
solvents. Suitable liquid solvents are essentially: aromatic compounds, such
as xylene, toluene or
alkylnaphthalenes, aliphatic hydrocarbons, such as cyclohexane or paraffins,
for example mineral
oil fractions, alcohols, such as butanol or glycol, and also ethers and esters
thereof, ketones, such
as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,
strongly polar solvents,
such as dimethylformamide and dimethyl sulphoxide, and also water. Liquefied
gaseous extenders
or carriers are to be understood as meaning liquids which are gaseous at
ambient temperature and
under atmospheric pressure, for example aerosol propellants, such as
halogenated hydrocarbons,
and also butane, propane, nitrogen and carbon dioxide. Suitable solid carriers
are: for example
natural ground minerals, such as kaolins, clays, talc, chalk, quartz,
attapulgite, montmorillonite or
diatomaceous earth, and ground synthetic minerals, such as finely divided
silica, alumina and
silicates. Suitable solid carriers for granules are: for example crushed and
fractionated natural
minerals, such as calcite, marble, pumice, sepiolite, dolomite, and also
synthetic granules of
inorganic and organic meals and also granules of organic material, such as
sawdust, coconut shells,
maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are:
for example nonionic
and anionic emulsifiers, such as polyoxyethylene fatty acid esters,
polyoxyethylene fatty alcohol
ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl
sulphates, arylsulphonates
and also protein hydrolysates. Suitable dispersants are: for example
lignosulphite waste liquors and
methylcellulose.
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Tackifiers, such as carboxymethylcellulose and natural and synthetic polymers
in the form of
powders, granules and lattices, such as gum arabic, polyvinyl alcohol and
polyvinyl acetate, or else
natural phospholipids, such as cephalins and lecithins and synthetic
phospholipids can be used in
the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron
oxide, titanium oxide
and Prussian blue, and organic dyes, such as alizarin dyes, azo dyes and metal
phthalocyanine
dyes, and trace nutrients, such as salts of iron, manganese, boron, copper,
cobalt, molybdenum and
zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of
active compound
combination, preferably between 0.5 and 50 per cent by weight.
The microbicidal compositions or concentrates used for protecting the
industrial materials
comprise the active compound or the active compound combination in a
concentration of from
0.005 to 95 per cent by weight, in particular from 0.1 to 50 per cent by
weight.
The application concentrations of the active compounds or the active compound
combinations to
be used depend on the nature and the occurrence of the microorganisms to be
controlled and on the
composition of the material to be protected. The optimum amount to be employed
can be
determined by test series. In general, the application concentrations are in
the range of from 0.001
to 10 per cent by weight, preferably from 0.01 to 5 per cent by weight, based
on the material to be
protected.
By using the active compound combinations or compositions according to the
invention, it is
possible to replace, in an advantageous manner, the microbicidal compositions
hitherto available
by more effective compositions. The compositions according to the invention
have good stability
and, in an advantageous manner, a broad activity spectrum.
Wood, timber products and wood/plastic composites which can be protected by
the active compound
mixtures according to the invention or compositions comprising them are, by
way of example:
construction timber, wooden beams, railway sleepers, bridge components,
jetties, vehicles made of
wood, boxes, palettes, containers, telephone poles, wood lagging, windows and
doors made of wood, ply
wood, medium density fibre board (MDF), chip board, oriented strand board
(OSB), waferboard,
laminated veneer lumber (LVL) or timber products which, quite generally, are
used in the construction
of houses or building joinery, and also wood/plastic composites.
The active compounds can be applied individually or as a finished mixture, in
the form of their
formulations or the use forms prepared therefrom, such as ready-to-use
solutions, suspensions,
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pastes, soluble powders. Application is in a customary manner by treating the
industrial material
with the individual active compounds or the finished mixture or with a
formulation or use form
prepared therefrom. If the materials to be protected are wood, timber products
or wood/plastic
composites, the application is by customary methods, for example by spraying,
painting, dipping,
industrial impregnation processes, for example vacuum, double vacuum or
pressure processes, and
by addition to the glue or by addition via the compounder or mixer, and also
via master batches.
A particularly effective protection of wood is achieved by industrial
impregnation processes, for
example by vacuum, double vacuum or pressure processes.
The present invention furthermore provides a method for protecting wood and
timber products,
where the wood or the timber product is impregnated with a synergistically
effective amount of
triadimefon and/or triadimenol and at least one of the insecticides mentioned
and at least one
diluent or solvent, if appropriate further auxiliaries and additives and also,
if appropriate, at least
one further active compound mentioned, by painting, spraying, vacuum, double
vacuum, pressure
or dipping processes. Here, the active compounds triadimefon and/or
triadimenol and at least one
of the insecticides mentioned can be employed either individually or as a
finished mixture.
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Biological Examples
The synergism was then determined using the method described by Kull et al.
(F.C. Kull,
P.C. Eismann, H.D. Sylvestrowicz, R.L. Mayer, Applied Microbiology 9, 538 to
541, 1961). Here,
the following relationships apply:
QA/ Qa + QB/ Qb = SI
Qa = Concentration of substance A which corresponds to the MIC
Qb = Concentration of substance B which corresponds to the MIC
QA = Concentration of substance A in the concentration of A/B which suppresses
microbial
growth
QB = Concentraiton of substance B in the concentration of A/B which suppresses
microbial
growth
SI = Synergistic index
SI = I means additivity
SI > I means antagonism
SI < 1 means synergism
Example 1:
Various concentrations of chlorfenapyr (A), triadimefon (B) and mixtures of
the two active
compounds mentioned were tested against the wood-destroying basidiomycete
Gloeophyllum
trabeum. Mycel pieces were punched out of a colony of the wood-destroying
organism and
incubated at 26 C on a nutrient agar which contained mould extract and
peptone. Subsequently,
the radial growth of the fungi threads with and without added active compound
was compared. The
stated minimum inhibitory concentration is the lowest concentration of active
compound in
succession at which the radial growth is suppressed completely.
Active Mixing ratio MIC SI
compound [ppm]
A > 20
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A:B 1:1 10 0.5
A:B 4:6 10 0.5
A:B 3:7 10 0.5
A:B 2:8 10 0.5
B 20
The determined index data show that the combination according to the invention
of triadimefon
with chlorfenapyr has, over wide ranges, a pronounced synergism.
Example 2:
Various concentrations of permethrin (A), triadimefon (B) and mixtures of the
two active
compounds mentioned were tested against the wood-destroying basidiomycete
Lentinus tigrinus.
Mycel pieces were punched out of a colony of the wood-destroying organism and
incubated at
26 C on a nutrient agar which contained mould extract and peptone.
Subsequently, the radial
growth of the fungi threads with and without added active compound was
compared. The stated
minimum inhibitory concentration is the lowest concentration of active
compound in succession at
which the radial growth is suppressed completely.
Active Mixing ratio MIC SI
compound [ppm]
A 20
A:B 4:6 10 0.8
A:B 3:7 6 0.51
A:B 2:8 6 0.54
A:B 1:9 6 0.57
B 10
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The determined index data show that the combination according to the invention
of permethrin
with triadimefon has, over wide ranges, a pronounced synergism.
Example 3:
Various concentrations of thiacloprid (A), triadimefon (B) and mixtures of the
two active
compounds mentioned were tested against the wood-destroying basidiomycete
Poria placenta.
Mycel pieces were punched out of a colony of the wood-destroying organism and
incubated at
26 C on a nutrient agar which contained mould extract and peptone.
Subsequently, the radial
growth of the fungi threads with and without added active compound was
compared. The stated
minimum inhibitory concentration is the lowest concentration of active
compound in succession at
which the radial growth is suppressed completely.
Active Mixing ratio MIC SI
Ippm]
compound
A 20
A:B 1:1 3 0.4
A:B 4:6 3 0.66
A:B 3:7 3 0.74
A:B 2:8 3 0.83
A:B 1:9 3 0.92
B 3
The determined index data show that the combination of thiacloprid with
triadimefon has, over
wide ranges, a pronounced synergism.
Formulation examples:
Example 1 (Technical-grade concentrate):
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10% of triadimefon, 0.5% of permethrin, 24.5% of texanol, 15% of ethoxylated
caster
oil, 15% of sodium rhizinolate/sodium dodecylbenzenesulphonate preparation,
35% of
dimethyl fatty amide
Example 2 (Technical-grade concentrate):
15% of triadimefon, 0.5% of chlorfenapyr, 22.5% of Texanol, 13% of sodium
rhizinolate/sodium dodecylbenzene sulphonate preparation, 14% of fatty acid
polyethylene glycol ether ester, 35% of dimethyl fatty amide
Example 3 (Technical-grade concentrate):
7.5% of triadimenol, 0.25% of bifenthrin, 16.25% of sodium rhizinolate/sodium
dodecylbenzene sulphonate preparation, 27% of ethoxylated caster oil, 49% of
Texanol
Example 4 (Emulsifiable concentrate):
5.0% of triadimefon, 0.1% of thiacloprid, 2.9% of sodium rhizinolate/sodium
dodecylbenzene sulphonate preparation, 27% of fatty acid polyethylene glycol
ether
ester, 65% of Texanol
Example 5 (Composition for impregnation):
0.3% of triadimenol, 0.01% of deltamethrin, 15% of Worleesol 31A (binder
concentrate), 0.8% of
Additol VXW 4940, 3.0% of ethoxylated caster oil, 3.0 % of Texanol, 77.89% of
water
Example 6 (Composition for impregnation):
0.4% of triadimefon, 0.01 % of cyfluthrin, 4.0% of alkyd resin, 4.0% of
Dowanol DPM,
91.59% of white spirit
Example 7 (Primer):
0.2% of triadimefon, 0.2% of tebuconazole, 0.4% of tolylfluanid, 0.05% of
cypermethrin, 6% of
Dowanol DPM, 10% of alkyd resin, 83.2% of white spirit
