NZ203546A - Fungicidal compositions containing dimethyl((1,2-phenylene)-bis-(iminocarbonothioyl)-bis-(carbamate) - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £03546 z 0354-6 NEW ZEALAND PATENTS ACT, 1953 No.: Prov. No. 203546 'r Date: 11 March 19 83 12 Mar, COMPLETE SPECIFICATION * 1984 FUNGICIDAL COMPOSITIONS X/We, IVON WATKINS-DOW LIMITED, a company incorporated under the laws of New Zealand, of 8 9 Pari tutu Road, New Plymouth, New Zealand, hereby declare the invention for which XX/ we pray that a patent may be granted to me/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- 2015546 This Invention Is concerned with fungicidal compositions and with a method for the prevention of decay or staining of wood.

Mould and sapstaln on wood are of world wide occurrence and may be found upon unseasoned material at any time of the year They cause degrade In timber because of a change In colour and are not permitted In the high quality grades.

Wood can be protected against mould, sapstaln and rot by rapid drying to a moisture content of less than 25$ and by protection against subsequent wetting. Unseasoned wood can be protected against sapstaln, mould and rot by using water soluble or water dispersable fungicidal solutions applied by a variety of methods known to the art Including dipping and spraying.

Early work In New Zealand comparing a number of chemicals (Orman H.R., NZFS, FRI, Forest Products Research Notes 1, (5), 1-15 (1954)) found none better than sodium pentachIorophenol. Butcher J.A., NZFS, FRI, Forest Products Branch, Report No. 406 (1972), screened a wide range of fungicidal agents and reported cls-N-(1,1,2,2-tetrachloroethyI) th ioH-4-cyclohexene-1,2-d icarboxlm Ide to be superior to sodium pentachIorophenol as an antisapstaln dip. Further work by Butcher J.A. and J. Drysdale, International Blodeterloration Bulletin, 1At (1), 11-19 (1978) testing twenty-six chemicals found only coppei—8-quinol Inate to be as cost effective as the above-mentioned treatments. Little work has been done tn New Zealand on the mixing of chemicals other than the mixing of sodium penta-chIorophenol with borax and cIs-N-C( 1,1,2,2-tetrachoroethyI)th Io]-4-cycIohexene-1,2-d icarboxlmIde and tetrachlorolsophthalonitrile. Overseas a number of mixtures are recorded: 3 203546 * v'-_,.

Roff J.W. et. al, Western Forest Products Laboratory, Technical Report No- 14R (1980), and Henningsson B., A.W.P.A. Joint Symposium 137-144 (1980).

According to the present Invention we have found that selected fungicides, which when applied alone do not have good activity In controlling mould and sapstaln, when formulated together have surprisingly good activity especially against mould organisms as well as against sapstaln and rot organisms.

It Is therefore an object of this Invention to provide fungicidal compositions and methods for the control of undesirable mould, stain and/or rot organisms In wood, especially on freshly sawn wood or wood which has not been dried to below 25% moisture content or wood which has been rewetted to above 25% moisture content.

In one aspect, the present Invention consists In a fungicidal composition which comprises substantially 1 part by weight of dimethyl [1,2-phenylene)bis- (iminocarbonothioyl)]bis-[carbamate] in admixture with from substantially ^/.c lb to substantially 4 parts by weight of a compound selected from octyl isothiazoline-3-one, 1,2-benzisothiazolone, and tetrachloroisophthalom'trile.

The compositions of the present Invention are conveniently adapted to the treatment of peeled or sawn timber to prevent the ravages of mould, stain and rot microorganisms. The fungicidal compounds In admixture In the novel fungicidal compositions appear to be mutually activating so that a greater than additive or synergistic result Is accomplished as regards the control of undesirable organisms, such as mould, stain and rot fungi. The compositions have a broader spectrum of activity than their component fungicides and thus j protection not only from stain and decay but also from moulds. It has 4 20354-6 also been found that the mixtures have low dermal toxicity, Increasing the safety In handling of the treated timber.

The compositions comprising the mixture of two fungicides are sufficiently Increased In effectiveness so as to permit the effective utilization of reduced amounts of the component fungicides, be they dimethyl 1,2-phenyIene)bIs-(Iminocarbonothloyl)3blsCcarbamateX octyl IsothiazolIne-3-one, 1,2-benz!so-thiazoione or tetrachloroisophthalonltrile. This permits a more economical use of fungicides than conventional compositions.

Dimethyl C(1,2-phenylene)bis-(iminocarbonothioyI)3~bIsEcarbamateJ has the formula: S 0 r II NH - C - NH II NH - C - NH C - OCH II II s o TetrachloroisophthaIonItr11e has the formula: CN CI Octyl IsothiazolIne-3-one has the formula: O S 1, 2-Benzisothiazolone has the formula: 0 203546 In formulating the compositions of the Invention, It Is preferable to maintain the proportions of substantially 1 part by weight of dimethyl [(1,2- weight of octyl isothiazoline-3-one or 1,2-benzisothiazolone or to 1 to 4 parts by weight of tetrachloroisophthalonitrile to provide an effective amount of the said mixture in the finished composition in order to maintain the desired synergistic effect.

The fungicidal compositions of the present Invention are conveniently stored and transported In the form of a powder, dispersion or emulslflable concentrate In a manner known to the art. Such concentrates normally contain from 40 to 60% by weight total active ingredients, preferably 10 to 45% by weight of dimethyl [(1,2-phenylene)bis-(iminocarbonothioyl)]bis[carbamate] and from 2 to 22.5% by weight, preferably 4 to 7% by weight, of octyl isothiazoline-3-one or 1,2-benzisothiazolone, or 10 to 4C" by weight of tetrachloroi sophthai oni tri 1 e.

For use as a wood protectant, the concentrate Is diluted with sufficient water to produce an aqueous suspension of the desired concentration, e.g. 0.1 to 1.0/S by weight of active ingredients.

In another aspect, the present Invention consists In a method for protecting wood against mould, sapstaln and/or rot which comprises applying to the wood surface a fungicidal composition of fhe present Invention.

The method of the Invention Is especially useful in protecting against mould, sapstaln and rot freshly sawn wood or wood which has not been dried to below 25$ moisture content or wood which has been rewetted to above 25$ moisture content. 6 203546 In general wood processing, plant applications and out In the field It Is usually preferred that the fungicidal compositions of the Invention are distributed over the whole surface of the wood to be protected from mould, stain or rot micro-organisms. It Is therefore desirable for the wood to be substantially free from these micro-organ Isms before application of the compositions of the Invention.

The compositions of the Invention can be applied to the wood to be protected either by spray, deluge or dip either momentary or plunge. It Is essential that all outside surfaces of the wood to be protected are coated with the composition dispersed in carrier and therefore the dip method of application Is preferred.

This Invention Is Illustrated In the following non-1 Imitative Examples: In the following Examples the active ingredient: Thlophanate methyl represents dimethyl C(1,2-phenyiene)bIs-(Imlnocarbono- th i oyI)H b i sCcarbamateH, ChIorothaIon I I represents tetrachIorolsophthaionItr11e, Octhallnone represents 2-n-octyI-4-isothiazolIne-3-one, and Proxel AB represents 1,2-benzIsothlazolone. ' 203546 Formulation Examples 1 to 3: Example..1 g /.litre Thlophanate methyl technical 179.6 (167) ChIorothaI oniI technical 350.6 (333) Lauryl Ether sulphate 50 NonyI phenolpolyoxyethylene ethanol 100 Water 394 Benton Ite clay 10 Silicone Defoamer 10$ emulsion 1 Example..^ Thlophanate methyl technical 479 445 Octhalfnone (45$) 122 55 NonyI phenolpolyoxyethyIene ethanol 100 Lauryl Ether sulphate 50 Benton Ite 10 Silicone Defoamer (10$) 1 Water Exarcple.,.3 Thlophanate methyl technical • 430 400 Proxel AB paste (33$) 300 100 NonyI phenolpolyoxyethyIene ethanol 100 DIethylene glycol monoethyl ether 25 Water 186 BentonIte 10 Defoamer 1 8 203546 Evaluation Examples 4 to 6 In the following Examples the method employed to test the fungicidal compositions was as follows: Branches of fresh p.lrnjs..nad.lata having a diameter of between 40-60 mm were sliced Into discs of 10mm thickness. Nine discs were treated with each concentration of each fungicidal composition and three were challenged with mould, three with stain and three with rot mIcro-organlsms. The discs were then placed In racks and held under conditions of 25°C and high humidity for three weeks. The order of treatment was dip in micro-organisms, drain, dip In composition, drain, place Into racks. After three weeks all discs were rated as folIows: Ra.t.Lna ^Contral, Clear no growth 1 100 Isolated patches predominantly around edges 2 75-100 Sparse and patchy cover overalI 3 50-75 Denser but patchy cover overalI 4 25-50 Dense overalI cover 5 0-25 The micro-organ Isms used In all cases were: Mou I d Ren.Ic.Ll.Llum^sp IrJcfiprierniaUlv.lr.lriae Stain Cera^ocxt.ISnSp P.Ip|prisaBpln.ea ftUemanlawSP 103546 Rot Con tophpraxpatsana Rpr.la^mont.Icola Pp.lys.tfctus., versicolor Epflies,o,Hvus In the Tables set out fn the following Examples the expected percent control and the percent Increase over expected control are computed using a calculation of synergistic response developed by Gowlng DP., 1960, Weeds, £, 379-391 and amended by Colby S.R., 1967, Weed Science, JJL, 20-22.

The actual calculations are:- (1) Control by chemical A or chemical B compared to "no chemical" control expressed as a percentage. (2) Expected controls = percent control by chemical A + percent control by chemical B MINUS percent»,cpnitrg.lrbynC^nemlicaJ,.AM«rtPer:cfin1:.nCor,tro.lMby..clieni,llcaJr.B 100 (3) Percent Increase over expected control = ,* x 100-100 expected control Examp.le„4 A series of trials were run using the method outlined earlier. A summary of results follows: 83 .00 67 83 50 67 75 75 75 75 67 42 50 58 50 0 0 24 49 8 41 24 49 58 0 0 Table 1: Compound Ratio % a. i.

Run Nur Thiophanate methyl + Octhalinone 2:1 0.25 1 Thiophanate methyl + Octhalinone 4:1 0.25 2 Thiophanate methyl + Octhalinone 4:1 0.25 3 Thiophanate methyl + Octhalinone 8:1 0.25 4 Thiophanate methyl + Octhalinone 4:1 0.25 Thiophanate methyl + Octhalinone 8:1 0.25 6 Thiophanate methyl + Octhalinone 8:1 0.1 7 Thiophanate methyl + Octhalinone 8:1 0.25 8 Thiophanate methyl + Octhalinone 8:1 0.15 9 Thiophanate methyl + Proxel AB 1:1 0.25 Thiophanate methyl + Proxel AB 3:1 0.25 11 Thiophanate methyl + Proxel AB 9:1 0.25 12 Thiophanate methyl + Chlorothalonil 1:1 0.2 Thiophanate methyl + Chlorothalonil 1:1 0.2 16 Thiophanate methyl + Chlorothalonil 1:2 0.2 17 Thiophanate methyl + Chlorothalonil 2:1 0.2 18 Thiophanate methyl + Chlorothalonil 1:4 0.2 19 Thiophanate methyl + Chlorothalonil 4:1 0.2 Thiophanate methyl 0.5 23 - - 0.25 24 - - 0.2 - - 0.14 26 - - 0.1 27 Octhalinone - 0.1 28 - - 0.05 29 Proxel AB - 0.25 Chiorothalonil - 0.2 31 Control - - 21 Control - - 22 203 54^ The control of stain and rot is important for the safe storage of freshly sawn timber. Mould control is Important from a cosmetic point of view. In this Example a number of tests are shown where the principal fungicides were tried in combination at different ratios. The composition of Thlophanate methyl plus Octhalinone at ratios of 4:1 and 8:1 when used at 0.25^ a.I. gives excellent control. Thlophanate meth/l plus Chlorothalonil at a ratio of 1:1 when used at 0.2% a.I. also gives good control of stain and mould with lesser control of rot. The fungicides when used alone do not demonstrate adequate control of sapstaln fungi and only In combination Is this control Increased. .12. 203546 Example 5 A conparison of Chlorothalonil and Thiophanate methyl alone and in admixture.

Table 2: Stain Control Chemical % a.i.

Chemi cal % a.i.

Ratio % Expected Control % Actual Control % Increase ove Expected C h1o rothaloni1 0.1 - - - - 0 0 - C h1o rothaloni1 0.133 - - - Chlorothalonil 0.067 - - - Chlorothalonil 0.16 - - -■ Chlorothalonil 0.04 Thiophanate methyl Thiophanate methyl Thiophanate methyl Thiophanate methyl Thiophanate methyl 0.1 0.067 0.133 0.04 0.16 - - 0 67 42 67 17 67 - Chlorothalonil 0.1 Thiophanate methyl 0.1 1:1 67 83 24 Chi orothalonil 0.133 Thiophanate methyl 0.067 2:1 52 92 77 Ch1o rothaloni1 0.067 Thiophanate methyl 0.133 1:2 69 67 - 4 Chlorothalonil 0.16 Thiophanate methyl 0.04 4:1 31 42 Ch1o rothalonil 0.04 Thiophanate methyl 0.16 1:4 67 83 24 203546 Table 3: Mould Control Chemical % a.i.

Chemical % a.i.

Ratio % Expected (2) Control % Actual Control % Increase over (3) Expected (1) - - - - - Chlorothalonil 0.1 - - - Chlorothalonil 0.133 - - - - - Ch 1 o rothalonil 0.067 - - - Ch1o rothalonil 0.16 - - - Chlorothalonil 0.04 Thiophanate methyl Thiophanate methyl Thiophanate methyl Thiophanate methyl Thiophanate methyl 0.1 0.067 0.133 0.04 0.16 - - 0 92 lb 92 8 92 - Chlorothalonil 0.1 Thiophanate methyl 0.1 1:1 93 100 7 Chlorothalonil 0.133 Thiophanate methyl 0.067 2:1 81 92 13 Chlorothalonil 0.067 Thiophanate methyl 0.133 1:2 95 100 6 Chlorothalonil 0.16 Thiophanate methyl 0.04 4:1 24 83 251 Chlorothalonil 0.04 Thiophanate methyl 0.16 1:4 92 100 * 9 203546 In this Example synergism Is demonstrated for two ratios, Chlorothalonil plus Thlophanate methyl at a ratio of 2:1 and Chlorothalonil plus Thlophanate methyl at a ratio of 4:1. A ratio of 1:1 of Chlorothalonil plus Thiophanate methyl shows no added effect, I.e. a straight additive effect, while a ratio of 1:2 Chlorothalonil plus Thlophanate methyl shows antagonisms. Clearly the ratio of the components In the mixture Is Important to gain a synergistic effect as demonstrated In the Examples. The composition must contain the Chlorothalonil plus Thlophanate methyl in a ratio of 2:1 to 4:1 to obtain a synergistic effect; a composition favouring the ratio of 4:1 Is desirable when mould Is the principal problem and a composition favouring the ratio of 2:1 when stain is the principal problem.

V. I r J • _ 15 _ 203546 Example 6 A trial to test synergism using the method as outlined earlier, was run using Thiophanate methyl and Octhalinone.

Table 4: Stain Control Chemical % a. i.

Chemical a.i.

Ratio % Expected control % Actual Control % Increase over expected Thiophanate methyl 0.14 - - - - 0 67 - Thiophanate methyl 0.13 - - - Thiophanate methyl 0.12 - - - Thiophanate methyl 0.1 Octhalinone Octhalinone Octhalinone Octhalinone 0.01 0.02 0.03 0.05 - - 42 0 17 0 8 - Thiophanate methyl 0.14 Octhalinone 0.01 16:1 67 58 -13 Thiophanate methyl 0.13 Octhalinone 0.02 8:1 79 75 - 5.3 Thiophanate methyl 0.12 Octhalinone 0.03 4:1 67 75 11 Thiophanate methyl 0.1 Octhalinone 0.05 2:1 46 58 24 Table 5: Mould Control Chemical % a.i.

Chemical % a.i.

Ratio % Expected Control % Actual Control % Increase over expected Thiophanate methyl 0.14 - - - - 0 33 - 'Thiophanate methyl 0.13 - - - - 0 Thiophanate methyl 0.12 - - - Thiophanate methyl 0.1 - - - - - Octhalinone 0.01 - - - - - Octhalinone 0.02 - - - - - Octhalinone 0.03 - - - Octhalinone 0.05 - Thiophanate methyl 0.14 Octhalinone 0.01 16:1 49 33 -13 Thiophanate methyl 0.13 Octhalinone 0.02 8:1 58 132 Thiophanate methyl 0.12 Octhalinone 0.03 4:1 50 50 0 Thiophanate methyl 0.1 Octhalinone 0.05 2:1 42 33 -21 * 203544 - 17 ~ Table 6: Rot Control Chemical % a.i.

Chemical % a.i.

Ratio % Expected Control % Actual Control % Increase over expected Thiophanate methyl 0.14 - - - - 0 50 - Thiophanate methyl 0.13 - - - Thiophanate methyl 0.12 - - - Thiophanate methyl 0.1 Octhalinone Octhal inone Octhal inone Octhalinone 0.01 0.02 0.03 0.05 - - 58 33 17 50 58 - Thiophanate methyl 0.14 Octhalinone 0.01 16:1 66.5 67 0.7 Thiophanate methyl 0.13 Octhalinone 0.02 8:1 65 75 Thiophanate methyl 0.12 Octhalinone 0.03 4:1 79 67 . -15 Thiophanate methyl 0.1 Octhalinone 0.05 2:1 82 42 -49 203546 In this Example of mixtures of Thiophanate methyl and Octhalinone, synergism Is demonstrated for particular ratios. However, the ratio Is very Important and different ratios are effective In controlling the different v groups of fungi. For the control of mould fungi a ratio of 8:1 of Thlophanate methyl and Octhalinone shows a high level of synergism while ratios either side I.e. 16:1 and 2:1 show a level of antagonism with a ratio of 4:1 showing no Improvement over a straight additive effect. For the control of stain fungi r the ratio of 4:1 or 2:1 of Thlophanate methyl plus Octhalinone showed a level of synergistic control while for rot control a ratio of 8:1 was synergistic.

Once again this Example demonstrate that a ratio of between 4:1 and 8:1 Thlophanate methyl plus Octhalinone Is needed for a greater than additive effect; the exact ratio combination of the two fungicides In the composition being determined by which group of fungi require control. r 203546

Claims (10)

WHAT WE CLAIM IS:

1. A fungicidal composition comprising substantially 1 part by weight of dimethyl [(1,2-phenylene)bis-(iminocarbonothioyl )]bis-[carbamate] in admixture with from substantially to substantially 4 parts by weight of a compound selected from octyl isothiazoline-3-one, 1,2-benzisothiazolone and tetrachloro-isophthalonitrile.

2. A composition according to claim 1 comprising substantially 1 part by weight of dimethyl [(l,2-phenylene)bis-(iminocarbono-thioyl )]bis-[carbamate] in admixture with to ^ Part by weight of octyl isothiazoline-3-one or of 1,2-benzisothiazolone.

3. A composition according to claim 1 comprising substantially 1 part by weight of dimethyl [(1,2-phenylene)bis-(iminocarbono-thioyl)]bis-[carbamate] in admixture with from 1 to 4 parts by weight of tetrachloroi'sophthalonitrile.

4. A composition according to any one of the preceding claims in the form of a powder, dispersion or emulsifiable concentrate.

5. A composition according to claim 4 comprising from 40 to 60% by weight total active ingredients. 203546 - 20 -

6. A composition according to claim 4 or claim 5 comprising from 10 to 45 $ by weight of dimethyl Cd ,2-pheny lene)bls-( Imfnocarbonothloy I )3bIs-Ccarbamate] and from 2 to 22.5 % by weight of octyl isothiazolirie-3-one or of 1,2-benzIsothIazolone.

7. A composition according to claim 4 or claim 5 comprising from 10 to 45 £ by weight of dimethyl 1,2-pheny lene) b I s—C !m Inocarbonoth loy I )bfs~Ccarbamate]] and from 10 to 45 % by weight of tetrachlorolsophthalonltrl le.

8. A composition according to any one of claims 1 to 3 In the form of an aqueous suspension.

9. A composition according to claim 8 comprising from 0.1 to 1.0 % by weight of active Ingredients.

10. A method for protecting wood against mould, sapstaln and/or rot which comprises applying to the wood surface a fungicidal composition as claimed In any one of the preceding claims 1 to 3, 8 and 9. NJLPATQfFomrJ . 10 JAN 1986