FUNGICIDAL COMPOSITION CONTAINING A GUANIDINE COMPOUND

SUBSTANCE FONGICIDE CONTENANT UN COMPOSE A BASE DE GUANIDINE

English Abstract

ABSTRACT OF THE DISCLOSURE
The present invention relates to fungicidal compositions com-
prising a quaternary ammonium compound and a guanidine component consisting
of a guanidated aliphatic diamine or polyamine. The compositions are par-
ticularly useful for the protection of wood and wood based materials against
wood destroying fungi.

Claims

THE EMBODIMENTS OF THE INVENTION IN which AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. Composition for the control of wood destroying fungi, comprising a)
a quaternary ammonium compund containing at least one higher aliphatic group having
from 6 to 24 carbon atoms and b) a guanidine component consisting of a guani-
dated aliphatic diamine or polyamine, or acid addition salt thereof said
guanidine component having the general formula
<IMG>
wherein X is hydrogen or a carboxamidine group, optionally substituted with
alkyl groups having 1 to 4 carbon atoms, R1 and R2 independent of each other
are aliphatic groups having 3 to 14 carbon atoms and n=0-6, wherein the
weight ratio of a) to b) is within the range 1:2 to 20:1.
2. A composition according to claim 1 characterized in that the
guanidine component is a diguanidated diamine.
3. A composition according to claim 2, characterized in that the
guanidine component has the general formula
X - HNR1 - NHR2 - NH-X
wherein X is a carboxamidine group, optionally substituted with alkyl groups
having 1 to 4 carbon atoms and R1 and R2 independent of each other are ali-
phatic groups having 3 to 14 carbon atoms.
4. A composition according to claim 1, characterized in that the
guanidine component is made up from 10-90 per cent by weight of guanidated
diamine, 20 to 60 per cent by weight of guanidated triamine and 10 to 60
per cent by weight of guanidated tetraamine or higher oligomers.
5. A composition according to claim 1, characterized in that the
guanidine component has a degree of guanidation exceeding 70 per cent.
6. A process for protecting wood and wood based materials against
wood destroying fungi said process comprising treating the materials with a
fungicidal composition comprising a) a quaternary compound containing at least

one higher aliphatic group having from 6 to 24 carbon atoms and b) a guanidine
component consisting of a guanidated aliphatic diamine or polyamine, or acid
addition salt thereof said guanidine component having the general formula
<IMG>
wherein X is hydrogen or a carboxamidine group, optionally substituted with
alkyl groups having 1 to 4 carbon atoms, R1 and R2 independent of each other
are aliphatic groups having 3 to 14 carbon atoms and n=0-6, wherein the
weight ratio of a) to b) is within the range 1:2 to 20:1.
11

Description

~ )16~5
The present invention relates to fungicidal compositions com-
prising both a) a quaternary arnmonium compound and b) a guanidine component
said component being a guanidated aliphatic diamine and/or a guanidated
aliphatic polyamine.
The components of the present compositions have previously each
separately been employed as fungicides. Quaternary ammonium compounds such ~ '
as alkylbenzyl dimethylammonium chloride have been used for protection of
wood, e.g. for protection against soft rot. Guanidated aliphatic diamines
and polyamines have predominantly been used in horticulture and agriculture ;
for control of soil and seedborne fungi.
It has now been found that mixtures of quaternary ammonium com-
pounds and guanidated amines not only give an additive effect but also a
synergistic effect. ~ixtures of active components according to -the inven-
tion give an unexpected prolongation and also a widening of the fungicidal
effect which cannot be attributed to an additive effect.
` The quaternary ammonium compounds useful in the compositions of
the invention can be represented by the general formula
R
R'- ~- R"
R"'
wherein at least one of the groups R is a higher carbon chain, i.e. a
straight or branched, substituted or unsubstituted aliphatic group having -
6 to 24 carbon atoms. As example of an inert substituent in the higher
aliphatic group can be mentioned an ether group. The quaternary ammonium
compounds contain one or two higher groups while the other substituents R
independent of each other are alkyl or hydroxyalkyl groups having 1 to 1~
carbon atoms or benzyl groups. Two of the other substituents can also form
a piperidine or morpholine eroup with the nitrogen atom. The anion is pref-
erably chloride but can of course be replaced by other ions such as bromide,
ethyl sulphate ion etc. The quaternary ammonium compound suitably contains
one or two alkyl groups having 6 to 24 carbon atoms and preferably 8 to 1~
carbon atoms. As examples of suitable fung~.cidal quaternary ammonium com-
-- 1 --
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pounds for use in the present compositions can be mentioned didecyl
dimethylammonium ch~oride, cetyl trimethylammonium chloride, alkyl ben~yl
dimetnylammonium chloride and other quaternary ammonium compounds wherein
the chain length distribution of the higher alkyl group or groups corre-
sponds to that of naturally occuring substances such as that of coconut
acid, cetyl dimethyl ethylammonium ethylsulphate etc.
~he guanidine component of the present compositions is at least
one guanidated aliphatic diamine or at least one guanidated aliphatic poly- -
amine, which includes triamines, tetraamines and higher oligomers or a mix-
ture of guanidated diamines and polyamines. Because of the base strength
of the guanidine groups the guanidated amines are generally present as acid
addition salts, e.g. chlorides, sulphates, nitrates, acetates, formates,
stearates, oleates etc.
The guanidine component can be represented by the general formula
X - HNRl - (~R2)n - N~I - X (I)
wherein X is hydrogen or a carboxamidine group, i.e. the group
H
-C \ . In the carboxamidine group one or several of the hydrogens
~H2
may be replaced b~ alkyl groups having 1 to 4 carbon atoms. Preferably X
as a carboxamidine group is unsubstituted. Rl and R2, independently o~
each other are aliphatic groups having 3 to 14 carbon atoms, suitably
alkylene groups having 6 to 12 carbon atoms such as hexyIene-, heptylene-,
octylene-, nonylene-, decylene-, dodecylene groups or cycloalkylene groups
such as cyclopentylene-, cyclohexylene-, cycloheptylene- or cyclooctylene
groups. Most preferably the alkylene groups contain 6 to 9 carbon atoms.
In the formula n=0-6, preferably 0-4. The groups R2 do not necessarily have
to be the same when n~l.
- When the guanidine component is a guanidated aliphatic diamine
it suitably has the general formula
- 2 -
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( )2 3 ( )2 (II)
~herein R preferably is hydrogen but also can be a lower alkyl group having
1 to 4 carbon atoms and R3 is an alkylene group having 3 to 1~ carbon atoms,
suitably 6 to 12 carbon atoms.
Guanidated aliphatic polyamines are compounds having the general
formula
X
X - HNR1 - (NR2)n -NH - X (III)
wherein X is hydrogen or a carboxamidine group, optionally substituted with
aIkyl groups having 1 to 4 carbon atoms, Rl and R2 independently of each
other are aliphatic groups having 3 to 14 carbon atoms, suitably 6 to 12
carbon atoms, and wherein n=1 6, preferably 1 to 4. The groups R2 do not
necessarily have to be the same when n>l.
As an example of a suitable guanldated aliphatic polyamine can be
mentioned the triamine with the formula
X - HNRl - NHR2 ~ NH - X
; wherein X are carboxamidine groups and Rl and R2 have the above given mean-
ing.
When the guanidine component is a guanidated aliphatic polyamine
it is preferably composed of a mixture of derivatives of the above formula
(III) having a degree of guanidation exceeding 30 % and preferably exceeding ;;
70 %. As has been mentioned the guanidine component is generally present as
an acid addition salt. -
A degree of guanidation exceeding 30 % for a mixture of deriva-
tives of formula (III) means that the total number of carboxamidine groups
in the mixture exceeds 30 % of the total number of N-atoms based on the mix-
ture of derivatives of the formula (III). In the present mixtures of
quaternary ammonium compounds and guanidine components the latter are suit-
ably mixtures of guanidated aliphatic diamines and guanidated aliphatic
polyamines.
The guanidine component hereby has a degree of guanidation exceed-
- 3 -
'~'. ' .

ing 45 %, suitably exceeding 70 ~ and preferably within the interval fo to
95 %. The component hereby consists of from 10 to 90 per cen~ by weight of
diamine, 20 to 60 per cent by weight of triamine and 10 to 60 per cent ~y
weight of tetraamine and higher oligomers. Suitably the guanidine component
is made up from 15 to 30 per cent by weight of diamine, 20 to 50 per cent by
weight of triamine, 30 to 60 per cent by weight of tetraamine and higher
oligomers and has a degree of guanidation within the interval of 70 to 95 %.
Particularly good results have been obtained with compositions
wherein the guanidine derivatives of the above formulae have alkylene groups
10 of eight carbon atoms.
Mixtures of guanidated aliphatic polyamines which contain ran-
domly guanidated nitrogen atoms have recently been developed. As no demands
on specific guanidation is required the mixtures can be prepared in a simple
manner starting for example from a technical mixture of amines which are
guanidated with cyanamide, urea- or thiourea derivatives to the desired de-
gree of guanidation. These mixtures can of course also contain guanidated
diamines.
In the compositions according to the invention the weight ratio
of quaternary ammonium compound to guanidine component is within the range
20 of from 1:2 to 20:1, preferably within the range of from 2:1 to 10:1. The
compositions can be prepared by simple mixing of the two active componen-ts,
preferably in water solutions although polar solvents also can be used.
The compositions can be used for agricultural and horticultural
purposes but are preferably used in different industrial applications.
- The compositions are particularly suitable as wood preservatives
for building and construction materials. It has been found that the com-
positions give an excellent protection against wood destroying fungi such as
mould, rot and blue fungi. A considerably prolonged effect is obtained by
the utilization of the co~bination of active ingredients compared with the
30 utilization of each of them separately. It has also been found that the
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protection against blue fungi is particularly improved with the composi-
tions. All kinds of wood and wood based materials which are susceptible to
wood destroying fungi can be protected by applying the present compositions
using conventional methods such as dipping, spraying, coating, impregnation.
The invention also relates to a process for protecting wood and
wood based materials against wood destroying fungi which comprises treating
the materials with a fungicidal composition comprising a quaternary ammoniurn
compound and a guanidine component consisting of a guanidated alipha-tic
diamine or polyamine, or acid addition salt thereof.
The two active components of the compositions are cationic and
t.hus a very good retention to the negatively charged cellulose material is
obtained. Additional substances for facilitating the retention of the com-
positions to wood are thus not necessary. Further the active components
are soluble in water so that the hydrocarbon solvents which are generally
used for wood preservatives and which are undesirable from a toxicological
point of view do not have to be used. The compositions can of course never-
theless form part of all conventional kinds of formulations including powder
formulations. The present compositions possess a further advantage compared
with generally used substances for wood protection, such as pentachloro-
phenols and bifluorides, in that the components have negligible vapour pres-
sures and thus do not give off vapours which is a considerable advantage
from a toxicological and environmental point of view.
The concentration of the active components in liquid formulations
for use as wood preservatives is generally within the range of from 0.1 to
10 per cent by weight. The concentration is however not critical but is
adapted with respect to the desired protection and the kind of wood.
The compositions according to the invention have both a prophy-
lactic and a curative effect and can beside the above mentioned application
also be used for disinfection of timber drying equipment and of buildings .
and other constructions which have been attacked by mould and rot. For
. .
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disinfection of damaged buildings the compositions in the form of solutions
or dispersions can be introduced into foundations, double flooring, walls
and other damaged places. The composition can be used for treatment of
foundations in order to protect binders used therein against attacks from
fungi and growth of fungi. They can also be used for fibre materials such
as paper and textiles and can hereby be inserted in different steps of the
respective production process, they can for example be added to a pulp sus-
pension at paper production.
The invention also relates to the compositions in combination with
diluents and additives known per se and it is also within the scope of the
invention that the compositions can form part of formulations containing
other known fungicidal and pesticidal substances.
The inventlon is further described in the following examples
which, however, are not intended to limit the same.
Example l
Fresh cut discs of pine having approximate dimensions of 5 cm
diameter and 1 cm thickness were dipped into a standard spore solution con-
taining mainly spores of Cladosporium ~erbarum, Pullularia Pullulans and
Ceratosystis Coerulem. The discs were thereafter allowed to dry for 1 min-
ute. A reference was taken and the other discs were during 30 seconds dip-
ped into treatment baths of water solutions having different concentrations
of quaternary ammonium compounds, guanidated amines and mixtures of these
according to the invention. A reference and two identically treated discs
were thereafter put into plastic bags which were closed and stored at room
temperature. Visual inspections of attack were made at different times
after the infection according to a scale 0-4 where 0 stands for no attack,
1 a tendency to attack, 2 attack, 3 severe attack and 4 very severe attack.
The following designations are used in the Table below:
a) alkylbenzyl dimethylammonium chloride wherein the number of carbon atoms
in the alkyl group essentially is 12-18.
~`..
- ~ - 6 -
.
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6~S
b) a guanidine component comprising 20 % n-octylene diamine, 40 % bis(8~
aminooctyl)-amine and 40 % higher oligomers, the mixture having a total de-
gree of guanidation of 82 %. The guanidine component was present as ace-
tate.
In the Table are given the assessments at each concentration of
the respective active substance in comparison with the corresponding refer-
ence for which the assessment is given after the stroke.
Time after Active substance~ per cent by weight in the
infection,
weeks treatment bath
a b a ~ b
:
1 % 2 % 4 % 0.2% o.4% 1 % 1%+0.2~ 2%+0.2%
2 2/3 2/3 1. 5/3 2/3 0/2. 5 0/3 0/0 0/0
4 3/4 3/4 2.5/3.5 2.5/4 0.5/3 o/4 0/2.5 0/2.5 ;;
g 4/4 3/4 2/l~ 3/4 2/4 2/4 1/4 0.5/4 ~;
It is evident from the results that the present compositions give
a better and longer protection than the components separately. Thus 1 % of -
the quaternary ammonium compound does not give any protection at all after
9 weeks, i.e. the entire disc is sub~ected to attack from fungi. In the
~same manner 0. 2% of the other component gives almost no protection after 9
~ .
weeks. The combination of these active substances give,~however, only a
tendency to attack after 9 weeks at a dosage of 1.0% ~ 0.2%.
Example 2
A corresponding treatment of pine discs as described in Example 1
was made, but with the difference that a solution of spores made up from
fungi from naturally infected wood was used for the infection. The solution
20 contained mainly spores from Penicillium, Trichoderma, Aspergillus and Pul-
lularia Pullulans.
The active substances tested were:
a) didecyl dimethylammonium chloride,
b) a guanidine component corresponding to that o~ Example 1.
The results of the visual inspections are given in comparison with
~ the respective reference.
`;` 7
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x
Time after Acti~e substance, per cent by weight in the
infection _reatment bath
a b a ~ b
1 % 2 % 4 % 0.2% 0.4% 1 % 1%~0.2% 2%~0.2%
2 0/0 o.5/o.5 0/0 0/3 0/3 0/3 o/1.5 o/l
4 2/2 1.5/2.5 o/2.5 1/l~ 1.5/4 o.5/4 0/3 0/3
9 4/4 3/4 1.5/4 3/4 3/4 2/4 3/4 1.5/4
Example 3
In this test a composi-tion comprising a) alkylbenzyl dimethyl-
ammonium chlorlde wherein the number of carbon atoms in the alkyl group
was essentiall~ 12 to 18 and b) diguanidated octylene diamine was studied.
Pine discs having a thickness of about 1 cm and a diameter of
about 6 cm were dipped into a spore solution containing spores of blue
fungi. The discs were thereafter allowed to dry for 5 to 10 seconds and
subsequently dipped into water solutions of the components a) and b) re-
spectively and compositions of these components. The discs were dippedinto the solutions for 5 to 10 seconds and thereafter dried for about 20
seconds. Two identically treated discs were placed in plastic bags to-
gether with a reference disc which had been dipped only into the spore so-
lution. The bags were closed and stored at room temperature.
Visual inSpeCtiOD of attack in relation to the reference disc
were made at different times after the infection according to a scale o-4
where 0 stands for no attack, 1 a tendency to attack, 2 attack, 3 severe
attack and 4 very severe attack. The results are shown in the Table below.
Time after in- Active substance, per cent by weight in the
fectiona days treatment bath
a b a ~ b
:
``` 1 % 2 % 0,2 % o,4 % 1 % + 0,2 % 2 % ~ o,4 %
26 3 3 3 3
"`, 33 4 3,5 3 3 0,5 o
~~~ 20 Example 4
~ ~ .
This test was carried out in the same manner as described in
- 8 -

$~
Example 3. The studied active components were a) didecyl dimethyl-ammoni~n-
chloride and b) acetate of bis(8-guanidino octyl) amine.
Time after in- Active substance, per cent by weight in
fection, days treatment bath
a b a + b
1 % 2 % 0.2 % o.l~ ~ 1 % + 0.2 % 2 % + 0.4%
26 3 3 3 1.5 0 0
33 3 3 3 2.5 0 0
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