CA1101605A - Fungicidal composition containing a guanidine compound - Google Patents
Fungicidal composition containing a guanidine compoundInfo
- Publication number
- CA1101605A CA1101605A CA302,900A CA302900A CA1101605A CA 1101605 A CA1101605 A CA 1101605A CA 302900 A CA302900 A CA 302900A CA 1101605 A CA1101605 A CA 1101605A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- guanidated
- guanidine
- groups
- guanidine component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
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.
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.
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-- ~k "
::~
.~5 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
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-- ~k "
::~
.~5 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 -`::
( )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-
( )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 ,,', -:
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 ,,', -:
- 4 -~ . , :: :: . ;. .
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 . .
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 . .
- 5 -, ! ' ; . .
s 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 -.
., .
s 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 -.
., .
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 ~
:;' 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 %
"`, 33 4 3,5 3 3 0,5 o ~~~ 20 Example 4 ~ ~ .
This test was carried out in the same manner as described in $~
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 '"
'~ " .
, ' ~'~
'`, `` ~
_ g _ ;` ,
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 ~
:;' 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 %
"`, 33 4 3,5 3 3 0,5 o ~~~ 20 Example 4 ~ ~ .
This test was carried out in the same manner as described in $~
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 '"
'~ " .
, ' ~'~
'`, `` ~
_ g _ ;` ,
Claims (6)
- 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 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 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 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE7705398-1 | 1977-05-10 | ||
| SE7705398A SE425043B (en) | 1977-05-10 | 1977-05-10 | FUNGICID COMPOSITION, PREFERRED FOR USE AS A THREE PROTECTIVE, CONTAINING AT LEAST ONE QUARTER OF AMMONIUM SUBSTANCE IN MIXING WITH AN AMINE COMPONENT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1101605A true CA1101605A (en) | 1981-05-26 |
Family
ID=20331269
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA302,900A Expired CA1101605A (en) | 1977-05-10 | 1978-05-09 | Fungicidal composition containing a guanidine compound |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS53139721A (en) |
| AT (1) | AT383770B (en) |
| CA (1) | CA1101605A (en) |
| CH (1) | CH639823A5 (en) |
| CS (1) | CS201005B2 (en) |
| DD (1) | DD135852A5 (en) |
| DE (1) | DE2820409C2 (en) |
| DK (1) | DK154534C (en) |
| FI (1) | FI62203C (en) |
| FR (1) | FR2390100A1 (en) |
| GB (1) | GB1581205A (en) |
| NZ (1) | NZ187128A (en) |
| PL (1) | PL111204B1 (en) |
| SE (1) | SE425043B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2483177A1 (en) * | 1980-05-29 | 1981-12-04 | Salkin Nicolas | NOVEL DISINFECTANT COMPOSITION COMPRISING A QUATERNARY AMMONIUM AND A HEXAMETHYLENE BIGUANIDE HYDROCHLORIDE OLIGOMER |
| JPS6028906A (en) * | 1983-07-26 | 1985-02-14 | Dainippon Ink & Chem Inc | Agricultural and horticultural fungicide |
| DK158570C (en) * | 1984-07-04 | 1990-11-12 | Gori As | FUNGICID AGENT FOR THE PROTECTION OF FRESH-CUTTED TREES AGAINST BLAST BINDING AND MOLD Fungi |
| JPS6157305A (en) * | 1984-08-29 | 1986-03-24 | 株式会社ザイエンス | Rotproof composition |
| DE3531356A1 (en) * | 1985-09-03 | 1987-03-12 | Hoechst Ag | MICROBICIDAL AGENTS BASED ON ALKYL-DI-GUANIDINIUM SALTS |
| DE4035772A1 (en) * | 1990-11-08 | 1992-05-14 | Bruno Wixforth | New fungicidal wood-dye - contg. water-insol. prod. of reaction of humic acid(s) with organic fungicide |
| CN1282698C (en) * | 2002-03-15 | 2006-11-01 | 上海塑杰科技有限公司 | Functional agglomerates of polyolefin as well as its preparing method and application |
| JP5101828B2 (en) * | 2006-03-22 | 2012-12-19 | 日本曹達株式会社 | Antifungal composition for wood and antifungal method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184035B (en) * | 1962-10-17 | 1964-12-23 | Hoechst Ag | Disinfecting mild detergents |
| DE1249577B (en) * | 1964-06-18 | 1967-09-07 | Telefunken Patentverwertungsgesellschaft M.B.H., Ulm/Donau | Method and device for recognizing the position of a flat object with respect to a feature applied to it |
| GB1274668A (en) * | 1968-06-10 | 1972-05-17 | Ici Ltd | Pesticidal compositions comprising aminoguanidines |
| SE370003B (en) * | 1971-05-18 | 1974-09-30 | Kema Nord Ab | |
| AT318152B (en) * | 1972-07-31 | 1974-09-25 | Hurka Wilhelm | Disinfectants |
| DE2330481A1 (en) * | 1973-06-15 | 1975-01-09 | Benckiser Gmbh Joh A | DISH AND RINSE AGENT FOR DISHES AND THE LIKE |
| SE417569B (en) * | 1975-10-22 | 1981-03-30 | Kemanobel Ab | Certain stated mixtures of guanidated aliphatic polyamines, or their acid addition salts, for use as pesticides and antimicrobial agents |
-
1977
- 1977-05-10 SE SE7705398A patent/SE425043B/en not_active IP Right Cessation
-
1978
- 1978-04-27 AT AT306478A patent/AT383770B/en not_active IP Right Cessation
- 1978-05-01 NZ NZ18712878A patent/NZ187128A/en unknown
- 1978-05-04 CS CS285778A patent/CS201005B2/en unknown
- 1978-05-06 PL PL20664678A patent/PL111204B1/en unknown
- 1978-05-08 FI FI781435A patent/FI62203C/en not_active IP Right Cessation
- 1978-05-09 FR FR7813616A patent/FR2390100A1/en active Granted
- 1978-05-09 DD DD20527878A patent/DD135852A5/en unknown
- 1978-05-09 CA CA302,900A patent/CA1101605A/en not_active Expired
- 1978-05-10 CH CH510078A patent/CH639823A5/en not_active IP Right Cessation
- 1978-05-10 DE DE19782820409 patent/DE2820409C2/en not_active Expired
- 1978-05-10 GB GB1883078A patent/GB1581205A/en not_active Expired
- 1978-05-10 DK DK206478A patent/DK154534C/en not_active IP Right Cessation
- 1978-05-10 JP JP5456278A patent/JPS53139721A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DK154534C (en) | 1989-04-17 |
| AT383770B (en) | 1987-08-25 |
| CS201005B2 (en) | 1980-10-31 |
| FI62203C (en) | 1982-12-10 |
| GB1581205A (en) | 1980-12-10 |
| SE425043B (en) | 1982-08-30 |
| DD135852A5 (en) | 1979-06-06 |
| JPS53139721A (en) | 1978-12-06 |
| DK206478A (en) | 1978-11-11 |
| NZ187128A (en) | 1980-03-05 |
| CH639823A5 (en) | 1983-12-15 |
| PL111204B1 (en) | 1980-08-30 |
| ATA306478A (en) | 1987-01-15 |
| JPS614367B2 (en) | 1986-02-08 |
| FI781435A (en) | 1978-11-11 |
| DE2820409A1 (en) | 1978-12-14 |
| SE7705398L (en) | 1978-11-11 |
| FR2390100A1 (en) | 1978-12-08 |
| DE2820409C2 (en) | 1981-12-03 |
| PL206646A1 (en) | 1979-05-21 |
| DK154534B (en) | 1988-11-28 |
| FR2390100B1 (en) | 1981-01-23 |
| FI62203B (en) | 1982-08-31 |
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Legal Events
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| MKEX | Expiry |