Note: Descriptions are shown in the official language in which they were submitted.
` 11768(~4
The invention is concerned with agents that can be
diluted with water, have a bactericidal and fungicidal action
and are suitable, especially in aqueous formulations, for
example, as wood preservatives, disinfectants, as biocides
for paint systems, and for the bactericidal and fungicidal
treatment of textiles, plastics materials, adhesives, build-
ing materials, paper, leather, drilling and cutting oils and
circulating cooling water.
The present invention provides a bactericidal or
fungicidal agent comprising: (a) a trialkyltin compound having
in the alkyl groups bonded to the tin atom a total number
of from 9 to 12 carbon atoms, or a triphenyl-tin compound,
excluding triorgan-tin halides, (b) an alkali metal salt of
N'-hydroxy-n-cyclohexyldiazenium oxide. The components ta)
and (b) are preferably present in a ratio of from 5:1 to 1:5
by weight, especially from 3:1 to 1:3, by weight, respectively.
The agents of the invention are especially suitable
for use in aqueous formulations together with customary
emulsifiers, and find application, more especially, for pro-
tecting wood. In the aqueous formulations the concentration
of active ingredient is preferably between 0.05 and 5% by
weight, and for protecting wood the concentration is prefer-
ably within the range of from 0.1 to 3% by weight.
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:1176804
The invention accordingly al~o provides an
aqueous formulation which contains a bactericidal or
fungicidal agent as defined above and water,
The high activity of triorganotin compounds
again~t microorganisms, for example harmful fungi and
bacteria, i9 known. This class of compounds generally
has its optimum action when the total number of carbon
atomq in the alkyl groupq bonded to th~ t , a~ola is f.~m
9 to t2. Shorter or longer alkyl group~ reduce the bio-
cidal activity. Although triorganotin compounds have arelatively broad range of action against different micro-
organisms, for example gram-negative bacteria and certain
blue fungi, their action is,however, comparatively weak.
DE-PS 1 024 743 describes another group of
biocides which is used, for the most part, as wood
preservativ,~. These are salts of N'-hydroxy-N-alkyl-
diazenium oxides in which the alkyl may be cycloalkyl.
In the case of these compounds, however, there is the
disadvantage that high concentrations are required for
use in protecting wood and their action is only slight
against fungi that discolour wood and against bacteria
that colonise wood.
For the~e reasons, there have been proposed
(DE-OS 2 336 290, DE-OS 2 341 882) mixtures of aluminium
~alts of ~'-hydroxy-N-alkyldiazenium oxide~ in which the
alkyl may be cycloalkyl with other special biocides to in-
crease the activity or broaden the range of action.
:1176804
- 4 -
Surprisingly, we have now found that mixtures
of trialkyltin compounds with alkali metal salts of
N'-hydroxy-N-cyclohexyldiazenium oxide have a synergistic
action, e~pecially against gram-negative bacteria and fungi
which belong to the class of the Ascomycetes and
Funai imperfecti and which are generally difficult to
combat. An increase in action has also been found
against gram-positive bacteria and against rurgi that
destroy wood.
The agents according to the invention can be used
especially in the form of aqueous formulations, and are
suitable, more especially, for the protection of wood,
for example fresh-cut wood which is readily infested by
bacteria and fungi such as those of the type Asperqillus
and of Trichoderma. The agents can likewise be used to
protect wood for building, the synergistic action of the
active ingredients being effective against fungi that
destroy wood and also against infestation by bacteria.
Bacteria do not decompose wood, but can, however, aid an
attack by fungi.
For use in aqueous formulations, the agentQ
according to the invention can be prepared in the form
of stable aqueous concentrates which contain emulsifiers
suitable for the purpose, preferably non-ionic emulsi-
fiers such, for example, a3 alkylarylpolyglycol ethers.The active ingredient mixture in such concentrates iq
present in a concentration of from 10 to 25 ~ by weight.
'.
_ 5 _ 11768~4
The concentrates can be diluted, without difficulty,
to provide stable solutions for use.
Furthermore, the agents according to the invention
are suitable for the biocidal treatment of aqueous
paint systems, for example dispersions, as pot preserva-
tive and protection against infestation of the paint by
bacteria and fungi, especially also against infestation
of aqueous wood-paint systems, for example alkyd resin
dispersions, by blue fungi.
The aqueous formulations can be used also for
the biocidal treatment of different materials such as
paper, cardboard, plastics materials, textiles, adhesives,
building materials and leather.
A further area of use in the treatment of
quantities of water against undesired microorganisms,
for example circulating cooling water, manufacturing
water in the case of paper production or drilling and
cutting oils.
According to the field of use in each case, the
concentrations of active ingredient may suitably be
within the range of from 0.1 to 5 % by weight for
protecting wood, from 0.05 to 3 % by weight for the
treatment of paintsystems, paper, textiles and
building materials and from 0,0001 to 0.2 % by weight
in the case of cooling and manufacturing water, and
drilling and cutting oils.
The invention further provides a ~ethod of
.....
- 6 - ~768~4
combating bacteria or fungi which comprises treating
a material or area infested with or liable to
infestation by bacteria or fungi wqth an agent or
aqueous formulation in accordance with the invention.
As the trialkyltin compound there may be used,
more especially, a tri-n-butyltin compound, for example,
tri-n-butyltin oxide, tri-n-butyltin linoleate, tri-n-
butyltin naphthenate ox tri-n-butyltin abietate. There
also come into consideration the tripropyltin compounds.
The alkyl radicals may be the sc~me or different provided
the total number of carbon atoms is from 9 to 12.
The alkali metal salt of N'-hydroxy-N-cyclohexyl-
diazenium oxide is preferably the potassium salt, but
there may also be mentioned the sodium and lithium salts.
The following Examples illustrate the invention,
the parts .md percentages being by weight unless
otherwise stated.
:~768(~4
-- 7 --
Example 1
Formulation containing 10 % of active ingredient
4 parts by weight of tri-n-butyltin oxide
20 parts by weight of a 30 % aqueous solution
of the potassium salt of
N'-hydroxy-N-cyclohexyl-
diazeni~ oxide
20 parts by weight of non-ionic emulsifier
(Marlowet ISM)
56 parts by weight of water
The components are homogenised by stirring and a
clear to very slightly turbid mixture is obtained which,
when diluted with tapwater to an approximate ratio of
1 : 50, yields stable, clear to slightly opalescent
preparations. The non-ionic emulsifier (Marlowet ISM)
is an alkylaryl polyglycol ether supplied by ~ASF.
Marlowet ISM is a Registered Trade Mark.
Example 2
Formulation containing 10 % of active ingredient
5.7 parts by weight of tri-n-butyltin linoleate
14.3 parts by weight of a 30 ~ aqueous soiution of
the potassium salt of ~'-
hydroxy-N-cyclohexyl-
diazenium oxide
21.5 parts by weight of non-ionic emulsifier
(Marlowet ISM)
58.5 parts by weight of water
....
~ i768~4
-- 8 --
The components are ho genised by stirring and
a clear to very slightly turbid mixture is obtained
which, when diluted with tapwater to an approximate
ratio of 1 : 50, yields stable, clear to slightly
opalescent preparations.
Example 3
Formulation containing 24 % of active ingredient
12 parts by weight of tri-n-butyltin naphthenate
40 parts by weight of a 30 % aqueous solution of
the potassium salt of ~'-
hydroxy-~-cyclohexyl-
diazenium oxide
48 parts by weight of non-ionic emulsifier
(Marlowet ISM)
The components are homogenised by stirring and
a clear to very slightly turbid mixture is obtained
which, when diluted with tapwater to an approximate
ratio of 1 : 100, yields stable, clear to slightly
opalescent preparations.
~1768(~4
g
Example 4
Formulation containing 15 % of active ingredient
_
6 parts by weight of tri-n-butyltin abietate
30 parts by weight of a 30 % agueous solution of
the potassium salt of N'-
hydroxy-N-cyclohexyl-
diazenium oxide
24 parts by weight of non-ionic emulsifier
(Marlowet ISM)
40 parts by weight of water
The components are homogenised by stirring and a
clear to very slightly turbid mixture is obtained
which, when diluted with tapwater to an approxlmate
ratio of 1 : 75 yields stable, clear to slightly
opalescent preparations.
~768~4
- 10 -
Table 1
-
For a comparison of action, circular paper filters
~diarneter 5.5 cm) were soaked with the aqueous solutions
given in detail below, dried in air, then placed in
Petri dishes on plate-count agar which had been innoculated
with suspensi'ons of bacteria, and incubated for 2 days
at +37C. The size of the inhibition zones around the
filters was then determined:
!
% by Inhibition zone~ in mm
10 Active weight
ingredient of active Bacillus Bacillu~ Proteu~
in solution ingredient subtilis mesentericus vulqaris
Tri-n-butyl- 1 12 - 15 12 - 15 5 - 7
tin oxide 0.5 10 - 12 12 - 15 3 - 5
0~2 10 - 12 10 - 12 0 - t
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
K salt of 1 0 - 1 2 - 4 0
N'-hydroxy- 0.5 0 0 - 1 0
~-cyclohexyl- 0.2 0 0 - 1 0
diazenium
oxide
Example 1 1 >15 >15 12 - 15
0.5 >15 ~15 8 - 10
0.2 10 - 12 ~15 6 - 8
Example 2 1 12 - 15 12 - 1512 - 15
0.5 10 - 12 10 - 1212 - 15
0.2 9 - 10 10 - 128 - 10
- 11 - 11768(~4
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- 13 - ~ ~76804
Table 3
In accordance with the method of Table 2, the
inhibition zone~ around the samples were determined:
% by Inhibition zones in mm
Active weight
5 ingredient of active Chaetomium Poria Lenzitis
in solution ingredient qlobosum monticula trabea
Tri-n-butyltin 0.5 8 - 10 7 - 9 10 - 12
oxide 0.2 6 - 8 5 - 7 6 - 8
Tri-n-butyltin 0.5 3 - 4 3 - 4 5 - 7
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 ~ - 2 2 - 3
K salt of 0.5 2 - 3 4 - 6 4 - 5
N'-hydroxy- 002 0 0 0
N-cyclohexyl
diazenium
oxide
Example 1 0.5 12 - 15 8 - 10 12 - 15
0.2 8 - 10 6 - 8 8 ~ 10
Example 2 0.2 3 - 4 3 - 4 4 - 6
Example 3 0.5 5 - 7 4 - 5 6 - 8
0.22 - 3 3 - 4 4 - 5
For a comparison of action, small blocks of pine
sapwood measuring 5 x 2.5 x 1,5 cm were soaked in the
following solutions of active ingredient:
A 2 % tri-n-butyltin naphthenate
B 2 % potassium salt of N'-hydroxy-N-cyclohexyl-
diazenium oxide
C 2 % the mixture of active ingredients specified
in Example 3
D without active ingredient.
1:176804
- 14 -
After drying and sterilisation, one small block in
. each case without active ingredient and with active
ingredient was inserted into a ~alle dish having biomalt
agar which had been sprayed with a suspension of spores
of the test fungi, and incubated for 10 weeks at +30C.
The growth of the fungi mycelium at and on the samples
was then assessed visually:
Inhibitory action of soaked small wood blocks a~ainst test
_________ _____________________________________ __________
fun~i in the Xalle dish test
___ ________________________
Take-up of Test funoi
active Trichoderma viride Pullularia
ingredient Pullulans
Soaking % by Growth of ¦ Growth of
solution weight the sample* I IZ* tne sample* IZ*
A 0.031 _ l1 - 2
D _ +++ 1
A 0.033 I . _ 0 - 1
D _ l +++
B 0.034 ~+ 0
20 D _ +++ 0
B 0.030 _ 1 - 2
D _ +++ 0
C 0.029 _ 4 - 5
D _ +++ 0
C 0.033 _ 3 - 4
D _ +++ 0
*) Growth of the sample - = no growth
+ = slight growth
. ++ = moderate growth
+++ = strong growth
IZ = Inhibition zone
around the sample
in ~
