GB1581205A

GB1581205A - Fungicidal composition

Info

Publication number: GB1581205A
Application number: GB1883078A
Authority: GB
Original assignee: Kemanobel AB
Current assignee: Kemanobel AB
Priority date: 1977-05-10
Filing date: 1978-05-10
Publication date: 1980-12-10
Also published as: DD135852A5; FI62203B; DE2820409A1; DK206478A; FI781435A; DK154534C; DK154534B; CH639823A5; JPS53139721A; PL111204B1; ATA306478A; PL206646A1; FR2390100A1; SE7705398L; JPS614367B2; DE2820409C2; NZ187128A; AT383770B; FI62203C; CA1101605A

Abstract

The fungicide contains, as active ingredient, a mixture of a quaternary ammonium compound having at least one aliphatic group having 6-24 C atoms, and a guanidine component in the form of at least one guanidated aliphatic di- and/or polyamine or an acid addition salt thereof, of the formula I, where the substituents have the meanings given in Patent Claim 1. The combination of these two active ingredients shows not only an additive, but also a synergistic activity with a substantially improved duration of action and a broader spectrum of action. The composition can be formulated as desired and is suitable for any use as fungicide, but particularly for the treatment of wood and wood-containing materials as a protection against wood-destroying fungi. <IMAGE>

Description

(54) FUNGICIDAL COMPOSITION (71) We, KEMANOBEL AB, a Swedish Body Corporate, of Box 11005, S100 61 Stockholm 11, Sweden, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to fungicidal compositions comprising both a) a quaternary ammonium compound and b) a guanidine component, said component being a guanidated aliphatic diamine and/or a guanidated aliphatic polyamine or an acid addition salt thereof.

The components of the present compositions have each previously been separately employed as fungicides. Quaternary ammonium compounds, such as alkylbenzyl dimethylammonium chloride, have been used for the protection of wood, e.g. for protection against soft rot. Guanidated aliphatic diamines and polyamines have predominantly been used in horticulture and agriculture for the control of soil and seedborne fungi.

It has now been found that certain mixture of quaternary ammonium compounds and guanidated amines not only give an additive effect but also a synergistic effect. Mixtures of active components according to the present invention give an unexpected prolongation and also a widening of the fungicidal effect which cannot be attributed to an additive effect.

The present invention provides a composition for the control of wood destroying fungi, comprising a) a quaternary ammonium compound containing at least one higher aliphatic group having from 6 to 24 carbon atoms attached to nitrogen 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 independently are aliphatic groups having 3 to 14 carbon atoms and n is from 0 to 6, wherein the weight ratio of (a) to (b) is from 1:2 to 20:1.

The quaternary ammonium compounds useful in the compositions of the invention can be represented by the general formula:

wherein at least one of the groups R, R', R" and R"' is a higher carbon chain, i.e. a straight or branched, substituted or unsubstituted aliphatic group having from 6 to 24 carbon atoms. As an example of an inert substituent in such higher aliphatic groups can be mentioned an ether group. The quaternary ammonium compounds preferably contain one or two higher groups while the other substituents are preferably each independently alkyl or hydroxyalkyl having from 1 to 4 carbon atoms or benzyl. Two of the other substituents can also form a piperidine or morpholine group with the nitrogen atom. The anion is preferably chloride, but can, of course, be replaced by other ions such as, for example, bromide or the ethyl sulphate ion. The quaternary ammonium compound preferably contains one or two alkyl groups having from 6 to 24 carbon atoms and preferably from 8 to 14 carbon atoms. As examples of suitable fungicidal quaternary ammonium compounds for use in the present compositions can be mentioned didecyl dimethylammonium chloride, cetyl trimethylammonium chloride, alkyl benzyl dimethylammonium chloride, and other quaternary ammonium compounds wherein the chain length distribution of the higher alkyl group or groups corresponds to that of naturally occurring substances such as that of coconut acid or cetyl dimethyl ethylammonium ethylsulphate.

The guanidine component of the present compositions is at least one guanidated aliphatic diamine or at least one guanidated aliphatic polyamine (triamines, tetraamines or higher oligomers) or a mixture of guanidated diamines and polyamines. Because of the base strength of guanidine groups the guanidated amines are generally present as acid addition salts thereof, e.g. chlorides, sulphates, nitrates, acetates, formates, stearates or oleates.

The guanidine component can be represented by the general formula:

wherein X is hydrogen or a carboxamidine group, i.e. the group

In the carboxamidine group one or several of the hydrogens may be replaced by alkyl groups having from 1 to 4 carbon atoms. Preferably X is an unsubstituted carboxamidine group and R, and R2 are each independently an aliphatic group having from 3 to 14 carbon atoms, suitably an alkylene group having from 6 to 12 carbon atoms such as hexylene, heptylene, octylene, nonylene, decylene or dodecylene or a cycloalkylene group such as cyclopentylene, cyclohexylene, cycloheptylene or cyclo-octylene. Most preferably such alkylene groups contain from 6 to 9 carbon atoms. In formula (I) n=O-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:

wherein R is preferably hydrogen, or it may be a lower alkyl group having from 1 to 4 carbon atoms, and R1 is an alkylene group having from 3 to 14 carbon atoms, suitably from 6 to 12 carbon atoms.

Guanidated aliphatic polyamines are compounds having the general formula:

wherein X is hydrogen or a carboxamidine group, optionally substituted with alkyl groups having from 1 to 4 carbon atoms, R, and R2 are each independently an aliphatic group having from 3 to 14 carbon atoms, suitably from 6 to 12 carbon atoms, and wherein n=l-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 guanidated aliphatic polyamine can be mentioned the triamine with the formula: X-HNR1-NHR2-NH-X, wherein groups X are carboxamidine groups and R1 and R2 are as defined above.

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 /n for a mixture of derivatives 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 mixture of derivatives of formula (III). In the present mixtures of quaternary ammonium compounds and guanidine components the latter are suitably mixtures of guanidated aliphatic diamines and guanidated aliphatic polyamines.

The guanidine component preferably has a degree of guanidation exceeding 45%, suitably exceeding 70%, and more preferably from 70 to 95%. Said component preferably consists of from 10 to 90 percent by weight of diamine, from 20 to 60 percent by weight of triamine and from 10 to 60 percent by weight of tetraamine and higher oligomers. Suitably the guanidine component is made up from 15 to 30 percent by weight of diamine, 20 to 50 percent by weight of triamine, 30 to 60 percent by weight of tetraamine and higher oligomers, and has a degree of guanidation of from 70 to 95%.

Particularly good results have been obtained with compositions wherein the guanidine derivatives of the above formulae have alkylene groups containing eight carbon atoms.

Mixtures of guanidated aliphatic polyamines which contain randomly guanidated nitrogen atoms have recently been developed. As no demands on specific guanidation are made in this invention such mixtures can be prepared for the present compositions in a simpler manner starting, for example, from a technical mixture of amines which are guanidated with cyanamide, urea or thiourea derivatives to the desired degree of guanidation. These mixtures can, of course, also contain guanidated diamines.

In the composition according to the present invention the weight ratio of quaternary ammonium compound to guanidine component is usually from 1:2 to 20:1, preferably from 2:1 to 10:1. The compositions can be prepared by simple mixing of the two active components, preferably in water solution (although polar solvents can also be used).

The compositions can be used for agricultural and horticultural purposes but are preferably used in different industrial applications.

The present compositions are particularly suitable as wood preservatives for building and construction materials. It has been found that the compositions give excellent protection against wood-destroying fungi such as mould, rot and blue fungi. A considerably prolonged effect is obtained by utilization of the combination of the present active ingredients compared with utilization of each of them separately. It has also been found that protection against blue fungi is particularly improved with the present compositions. 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, and/or impregnation.

The invention thus also includes a process for protecting wood and woodbased materials against wood-destroying fungi, which process comprises treating said wood or materials with a fungicidal composition of the invention.

The two active components of the present compositions are cationic and thus very good retention to negatively charged cellulose material is obtained. Additional substances for facilitating the retention of the present compositions onto wood are thus not necessary. Furthermore, 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 present compositions can, of course, nevertheless form part of all kinds of conventional formulations including powder formulations. The present compositions possess a further advantage compared with generally used substances for wood protection, such as pentachlorophenols and bifluorides, in that the components have negligible vapour pressures 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 from 0.1 to 10 percent by weight. The concentration is, however, not critical but may be adapted with respect to the desired degree of protection and the kind of wood being protected.

The compositions according to this invention have both a prophylactic and a curative effect and can, besides the above-mentioned application, also be used for the disinfection of timber drying equipment and buildings and other constructions which have been attacked by mould and rot. For the disinfection of damaged buildings, the compositions can be in the form of solutions or dispersions to be introduced into foundations, double flooring, walls and/or other damaged places.

The compositions can be used for the treatment of foundations in order to protect binders used therein against attacks from fungi and the growth of fungi. The present compositions can also be used for fibre materials such as paper and textiles and can be included in different steps of the respective production process (they can, for example, be added to a pulp suspension during paper production).

The invention also includes the compositions in combination with diluents and additives known per se, and it is also within the scope of the present invention that the present compositions can form part of formulations containing other known fungicidal and pesticidal substances.

The invention will now be further described and illustrated by way of the following Examples.

Example 1 Fresh cut discs of pine having approximate dimensions of 5 cm diameter and 1 cm thickness were dipped into a standard spore solution mainly containing spores of Cladosporium Herbarum, Pullularia Pullulans and Ceratosystis Coerulem.

The discs were thereafter allowed to dry for 1 minute. A reference was taken and the other discs were dipped for 30 seconds 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 is essentially 12-18; and b) a guanidine component comprising 20% n-octylene diamine, 40 bis(8 aminooctyl)-amine and 40% higher oligomers, the mixture having a total degree of guanidation of 82%. The guanidine component was present as acetate.

In the Table given the assessments are at each concentration of the respective active substance in comparison with the corresponding reference for which the assessment is given after the stroke.

Active Substance, Percent by Weight in the Treatment Bath Time after infection, a b a+b weeks 1% 2% 4% 0.2 0.4 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 0/4 0/2.5 0/2.5 9 4/4 3/4 2/4 3/4 2/4 2/4 1/4 0.5/4 It is evident from the results that the present compositions give 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 subjected to attack from fungi. In the same manner 0.2 /n of the other component gives almost no protection after 9 weeks. The combination of these active substances gives, however, rise to a tendency only 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 carried out, but with the difference that a solution of spores made up from fungi from naturally infected wood was used for the infection. The solution mainly contained spores from Pinicillium, Trichoderma, Aspergillus and Pullularia Pullulans.

The active substances tested were: a) didecyl dimethylammonium chloride; and b) a guanidine component corresponding to that of Example 1.

The results of the visual inspections are given in comparison with the respective reference.

Active Substance, Percent by Weight in the Treatment Bath Time after infection a b a+b weeks 2 1 2% 4% 0.20/, 0.4 1% 1%+0.2 2+0.2 4 0/0 0.5/0.5 0/0 0/3 0/3 0/3 0/1.5 0/1 9 2/2 1.5/2.5 0/2.5 1/4 1.5/4 1.5/4 0/3 0/3 4/4 3/4 1.4/4 3/4 3/4 2/4 3/4 1.5/4 Example 3 In this test a composition comprising a) alkylbenzyl dimethylammonium chloride wherein the number of carbon atoms in the alkyl group was essentially from 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), respectively, and compositions of these components. The discs were dipped into the solutions for 5 to 10 seconds and thereafter dried for about 20 seconds. Two identically treated discs were placed in plastic bags together with a reference disc which had been dipped only into the spore solution. The bags were closed and stored at room temperature.

Visual inspections of attack in relation to the reference disc were made at different times after the infection according to a scale 04 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.

Active Substance, Percent by Weight in the Treatment Bath Time after infection, a b a+b days 1% 2/n 0.2% 0.4 l%+0.2% 2+0.4 3 3 3 3 0 4 3.5 3 3 0.5 Example 4 This test was carried out in the same manner as described in Example 3. The active components studied were a) didecyl dimethylammonium chloride and b) acetate of bis(8-guanidino octyl) amine.

Active Substance, Percent by Weight in the Treatment Bath Time after infection, days a b a+b 1% 2% 0.2% 0.4% 1%+0.2% 2%+0.4% 26 3 3 3 1.5 0 0 33 3 3 3 2.5 0 0 WHAT WE CLAIM IS: 1. A composition for the control of wood destroying fungi, comprising a) a quaternary ammonium compound containing at least one higher aliphatic group having from 6 to 24 carbon atoms attached to nitrogen 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

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

The results of the visual inspections are given in comparison with the respective reference.

Active Substance, Percent by Weight in the Treatment Bath Time after infection a b a+b weeks

2 1 2% 4% 0.20/, 0.4 1% 1%+0.2 2+0.2

4 0/0 0.5/0.5 0/0 0/3 0/3 0/3 0/1.5 0/1

9 2/2 1.5/2.5 0/2.5 1/4 1.5/4 1.5/4 0/3 0/3 4/4 3/4 1.4/4 3/4 3/4 2/4 3/4 1.5/4 Example 3 In this test a composition comprising a) alkylbenzyl dimethylammonium chloride wherein the number of carbon atoms in the alkyl group was essentially from 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), respectively, and compositions of these components. The discs were dipped into the solutions for 5 to 10 seconds and thereafter dried for about 20 seconds. Two identically treated discs were placed in plastic bags together with a reference disc which had been dipped only into the spore solution. The bags were closed and stored at room temperature.

Visual inspections of attack in relation to the reference disc were made at different times after the infection according to a scale 04 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.

Active Substance, Percent by Weight in the Treatment Bath Time after infection, a b a+b days 1% 2/n 0.2% 0.4 l%+0.2% 2+0.4

3 3 3 3 0

4 3.5 3 3 0.5 Example 4 This test was carried out in the same manner as described in Example 3. The active components studied were a) didecyl dimethylammonium chloride and b) acetate of bis(8-guanidino octyl) amine.

Active Substance, Percent by Weight in the Treatment Bath Time after infection, days a b a+b 1% 2% 0.2% 0.4% 1%+0.2% 2%+0.4%

26 3 3 3 1.5 0 0

33 3 3 3 2.5 0 0 WHAT WE CLAIM IS: 1. A composition for the control of wood destroying fungi, comprising a) a quaternary ammonium compound containing at least one higher aliphatic group having from 6 to 24 carbon atoms attached to nitrogen 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, Rl and R2 independently are aliphatic groups having 3 to 14 carbon atoms and n is from 0 to 6, wherein the weight ratio of (a) to (b) is from 1:2 to 20:1.
2. A composition as claimed in Claim 1, wherein the quaternary ammonium compound contains, attached to the nitrogen atom, one or two straight or branched, substituted or unsubstituted aliphatic groups having from 6 to 24 carbon atoms, the other group(s) attached to the nitrogen atom being alkyl or hydroxyalkyl having from 1 to 4 carbon atoms or benzyl or two of said other groups form a piperidine or morpholine group with the nitrogen atom.
3. A composition as claimed in Claim 1 or Claim 2, wherein the anion of the quaternary ammonium compound is chloride, bromide or an ethyl sulphate ion.
4. A composition as claimed in Claim 1, wherein the quaternary ammonium compound is one referred to specifically hereinbefore.
5. A composition as claimed in any preceding claim, wherein X is an unsubstituted carboxamidine group.
6. A composition as claimed in any preceding claim, wherein at least one of R and R2 is an alkylene group having from 6 to 12 carbon atoms.
7. A composition as claimed in any preceding claim, wherein n is 0-4.
8. A composition as claimed in any preceding claim, wherein n > l and the groups R2 are not all the same.
9. A composition as claimed in any preceding claim, wherein the guanidine component is a diguanidated diamine.
10. A composition as claimed in any one of Claims 1 to 4, wherein the guanidated component is a guanidated diamine having the formula (II) given hereinbefore.
11. A composition as claimed in any one of Claims 1 to 4, wherein the guanidine component is a guanidated aliphatic polyamine of formula (III) given hereinbefore.
12. A composition as claimed in any one of Claims 1 to 4, wherein the guanidine component has the general formula: X-HNR1-NHR2-NH-X, wherein X is a carboxamidine group optionally substituted with at least one alkyl group having from 1 to 4 carbon atoms and Rl and R2 are each independently an aliphatic group having from 3 to 14 carbon atoms.
13. A composition as claimed in Claim 12, wherein the guanidine component is a mixture of polyamines of formula (III) having a degree of guanidation exceeding 30%.
14. A composition as claimed in any one of Claims 1 to 4, wherein the guanidine component as made up from 10 to 90 percent by weight of guanidated diamine, from 20 to 60 percent by weight of guanidated triamine and from 10 to 60 percent by weight of guanidated tetraamine and/or higher oligomers.
15. A composition as claimed in Claim 14, wherein the guanidine component is made up from 15 to 30 percent by weight of guanidated diamine, from 20 to 50 percent by weight of guanidated triamine and from 30 to 60 percent by weight of guanidated tetraamine and/or higher oligomers.
16. A composition as claimed in any one of Claims 1 to 15, wherein the guanidine component has a degree of guanidation exceeding 70 percent.
17. A composition as claimed in Claim 16, wherein the degree of guanidation is from 70 to 95 percent.
18. A composition as claimed in any one of Claims 1 to 17, wherein the guanidine component has been made from a mixture of amines by guanidation with cyanamide or a urea or thiourea derivative.
19. A composition as claimed in any one of Claims I to 18, wherein the guanidine component is present as an acid addition salt.
20. A composition as claimed in Claim 19, wherein the salt is a salt of hydrochloric acid, sulphuric acid, nitric, acetic acid, formic acid, stearic acid or oleic acid.
21. A composition as claimed in any one of Claims I to 20, wherein the weight ratio of quaternary ammonium compound to guanidine component is from 2:1 to 10:1.
22. A composition as claimed in any one of Claims 1 to 21 and in the form of a liquid formulation.
23. A composition as claimed in Claim 22, wherein the active components of the composition are present at a concentration of from 0.1 to 10 percent by weight.
24. A composition as claimed in any one of Claims 1 to 22 also containing a diluent or other additive.
25. A composition as claimed in Claim 24, wherein at least one other fungicidal or pesticidal substance is present.
26. A composition as claimed in Claim 1 and substantially as hereinbefore described in any one of the Examples.
27. A process for preserving or protecting a fibre material, wood or a woodbased material, or for disinfecting timber equipment or any other article or a building which has been attacked by mould and/or rot, which process comprises administering to the fibre material, wood material, equipment, article or building an effective amount of a composition as claimed in any one of Claims 1 to 26.
28. A process as claimed in Claim 27 when used in protecting wood and/or a wood-based material against wood-destroying fungi.
29. A process as claimed in Claim 27 and substantially as hereinbefore described.
30. A process as claimed in Claim 27 and substantially as hereinbefore described in any one of the Examples.
31. A fibre material, wood or a wood-based material which has been preserved or protected by the application thereto of a process as claimed in Claim 27 or Claim 28.