NZ331830A

NZ331830A - Synergistic biocidal compositions comprising prochloraz and a triazole

Info

Publication number: NZ331830A
Application number: NZ33183098A
Authority: NZ
Inventors: Peter James Hayward; George William Mason; Wallace J Rae; John Doyle
Original assignee: John Doyle; George William Mason; Peter James Hayward; Wallace J Rae
Priority date: 1998-09-11
Filing date: 1998-09-11
Publication date: 2000-09-29

Abstract

This microbiocidal composition, which is useful in inhibiting the growth of fungi, comprises Prochloraz and one of triadimefon, proficonazole or 2-n-octyl-3-isothiazalone in a weight ratio of 32:1 to 1:16.

Description

<div class="application article clearfix" id="description"> No: 331830 Date: 11 September 1998 NEW ZEALAND Patents Act 1953 COMPLETE SPECIFICATION IMPROVEMENTS IN MICROBIOCIDAL COMPOSITIONS APPLICATIONS AND METHODS OF USING SAME We, PETER JAMES HAYWARD a New Zealand citizen of Plymouth Road, R D 4, New Plymouth, New Zealand, GEORGE WILLIAM MASON, a New Zealand citizen of Sutton Road, R D 4, New Plymouth, New Zealand, WALLACE J RAE, a New Zealand citizen of 8 Mahoe Street, New Plymouth, New Zealand and JOHN DOYLE, a New Zealand citizen of 35 Ngaio Street, New Plymouth, New Zealand 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 -1- p.cLtuiUAL PRUHtRTY OFFICE I OF N1. I 13 SEP W99 j L REHfi \/pp I 2 This invention concerns microbiocidal compositions and more particularly microbiocidal compositions which are intended to provide more effective and broader control of micro-organisms in various industrial systems and for household products, agricultural products, and biomedical products, etc. In particular, the present invention relates to the use of a composition of a carbamoyl imidazole compound, an example being N-propyl-N-(2-(2,4,6-trichlorophenoxy) ethyl)-imidazole-l-carboximide, hereafter referred to as prochloraz; with one or more of the following compounds: A triazole derived fungicide, an example being 1—(2—(2,4— dichlorophenyl)-4-propyl-l,3-dioxolan-2-ylmethyl)-1H-1,2, 4-triazole, hereafter referred to as propiconazole or 1-(4-chlorophenoxy)-3,3-dimethyl-l-(1H-1,2,4-triazol-l-yl) =butan-2-one, hereafter referred to as triadimefon; or a 2-n-octyl-3-isothiazalone compound. The term "microbiocidal" (or "antimicrobiocidal" or "biocidal") as used herein is intended to encompass, but is not restricted to, all fungi and bacteria causing rot, mildew, stain or mould. It is the principal object of this invention to provide synergistic compositions which overcome disadvantages of known microbiocidal compositions. spechis 2<l/08/99 We have found that compositions formed from guanidine type compounds and one or more of the specified secondary compounds (supra) unexpectedly afford synergistic antimicrobial activity against a wide range of microorganisms: the disruptive action on the organisms by the two compounds together is unexpectedly greater than the sum of both compounds taken alone. This synergy does not arise from the expected activity of the components nor from the expected improvement in activity. As a result of the synergy, the effective dose required can be lowered, which is not only more economical but also increases safety margins. The synergistic compositions of the present invention provide more effective and broader control of microorganisms in a number of systems. The present invention thus provides a composition having microbiocidal activity which includes Prochloraz and a second component selected from one or more of the group consisting of Propiconazole, Triadimefon or 2-n-octyl-3-isothiazalone and other known chemicals with funcidial activity; wherein the weight ratio of Prochloraz to the second component is from about 150:1 to 1:250. According to one broad aspect of the invention there is provided a microbiocidal composition including Prochloraz as a first component and a second component which includes either triadimefon, propiconazole or 2-n-octyl-3-isothiazalone, wherein the weight ratio of first component to second component is in ^NTELLECTUAL^O PERTY 0 p OF N.Z. | r SPEC 111 8 2 4 AUG 2000 f 23/08/00 the range of from substantially 32:1 to substantially 1:16. Preferably the weight ratio of first component to second component is in the range of from substantially 32:1 to substantially 1:2. The invention also provides a microbiocidal product containing from substantially 5 to substantially 30% by weight of the composition The product can be incorporated into or onto a locus in the form of an aqueous medium, the composition being additionally contained in an emulsifier and water. The invention further provides a microbiocidal composition which comprises Prochloraz as a first component and a second component which comprises triadimefon, propiconazole or 2-n-octyl-3-isothiazalone as the secondary compounds, where in the weight ratio of the first component to second component is in the range of from 2:1 to substantially 1:31. The weight ratio of the first component to second can be in the range of from substantially 2:1 to substantially 1:2. The invention provides a microbiocidal composition which comprises Prochloraz as a first component and a second component of which comprises triadimefon, propicanazole or 2-n-octyl-3-isothiazalone, wherein the weight ratio of INTELLECTUAL'PROPEWY ... OF N.2. 2 h AUG 2090 ; 23/08/00 RECEIVED I 5 first component to second component is in the range of from substantially 4:1 to substantially 1:16. The weight ratio of first component to second component can be in the range of from substantially 4:1 to substantially 1:1.25 and preferably from substantially 5 to substantially 30% of the composition. The invention provides a microbiocidal product containing a composition according to any of the preceding broad aspects with an emulsifier and water. A method for inhibiting the growth of fungi, particularly wood destroying fungi or wood staining or moulding fungi in or on a locus subject to contamination by bacteria, fungi, or algae, which comprises incorporating onto or into the locus, an amount of the composition of any of the preceding broad aspects which is effective to effect adversely the growth of the fungi. Preferably the locus is an aqueous medium, and the composition additionally contains an emulsifier and water. Applications of the synergistic antimicrobial compositions of the present invention include but are not limited to: inhibiting the growth of bacteria and fungi in aqueous paints and coatings, adhesives, sealants, latex emulsions, and joint cements; preserving cutting SPEC 1118 2-J/0S/99 6 fluids, controlling slime-producing bacteria and fungi in pulp and paper mills and cooling towers; as a spray or dip treatment for textiles and leather to prevent mould growth; protecting paint films, especially exterior paints, from attack by fungi which occurs during weathering of the paint film; preventing bacterial and fungal growth in paper coatings and coating processes; controlling bacterial and fungal growth and deposits during the manufacture of various specialty boards, eg cardboard, fibre board, plywood, oriented strand board, laminated veneer lumber, laminated lumber and particle board; preventing sap stain discolouration on freshly cut wood of various kinds; preventing rot and other fungal degrade on and in dry cut wood of various kinds; inhibiting the growth; inhibiting the growth of harmful bacteria, yeasts, fungi on plants, trees, fruits, seeds, or soil; preserving agricultural formulations, and the like. The compositions of the invention may be added separately to any system or may be formulated as a simple mixture comprising its essential ingredients, and if desired a suitable carrier or solvent, or an aqueous emulsion or dispersion. The invention also provides a method of inhibiting the growth of fungi, in a locus subject to contamination by fungi, which comprises incorporating into or onto the locus in an amount which is affective to adversely affect sriiC'l 118 24/08 99 7 the growth of fungi any of the compositions defined above. The composition of the invention can be formulated as a solution in a wide range of organic solvents. The solutions generally contain about 5 to 60% by weight of the active composition. It is generally more convenient to provide the compositions in a water-diluted form; this may be accomplished by adding emulsifier to the organic solution followed by dilution with water. In general, the weight ratio of the guanidine type compound to the second component in the 'composition may be in the range of from about 150:1 to about 1:250. Other specific and preferred ratios are given in the examples. The synergism of two-component compositions is demonstrated by testing a wide range of concentrations and ratios of compounds, generated by two-fold serial dilutions in a Malt Agar (Gibco) growth medium of a microbiocide in one dimension and another microcide in the second dimension, against fungi Coriolus versicolor, Tyromyces palustris, Rlternaria sp, Ophiostoma sp., Diplodia sp. , or Penicillium sp. Each test tube was inoculated to make about 5 x 10 fungi per ml. The lowest concentrations of each compound or mixtures to inhibit visible growth (turbidity) at 30°C for the fungi for 7 days were taken as the minimum inhibitory SPEC 1118 24, OR/99 8 concentration (MIC). The MIC were taken as end points of activity. End points for the mixtures of compound A(Guanadine component) and Compound B (second Component microbiocide) were then compared with the end points for the guanadine component A alone and compound B alone. Synergism was determined by a commonly used and accepted method described by Kull, F. C'.; Eisman, P. C.; Sylwestrowicz, H. D. and Mayer, R. L. in Applied Microbiology 9:538-541 (1961) using the ratio determined by Qa/QA+Qb/QB=^Synergy Index (SI) wherein QA= concentration of compound A in parts per million (ppm), acting alone, which produced an end point. Qa= concentration of compound A in ppm, in the mixture which produced an end point. QB= concentration of compound B in ppm, acting alone which produced an end point. Qb= concentration of compound B in ppm , in the mixture which produced an end point. When the sum of Qa/QA and Qb/QB is greater than one, antagonism is indicated. When the sum is equal to one additivity is indicated, and when less than one synergism is demonstrated. The test results for demonstration of synergism of microbiocide combinations are shown in tables 1 to 11. Each table concerns the combination of the Prochloraz SFRCIMS 2.1/08/99 9 component and one other secondary compound..., and shows: 1. the identity of the second microbicide (Compound B) . 2. test against Coriolus versicolor, Tyromyces palustris, hlternaria sp, Ophiostoma sp. , Diplodia sp., or Penicillium sp 3. the end-point activity in ppm measured by MIC for compound A alone(QA), for compound B alone (QB) for compound A in the mixture(Qa) or for compound B in the mixture (Qb). 4. the calculation of synergy index (SI) based on the formula the guanidine compound (compound A) to Compound B in the particular combination (A: B) . 5. the range of weight ratios for synergism and the preferred weight ratios. It will be appreciated by those skilled in the art that the ratios given are approximate only. The MIC values of each compound tested alone (QA or QB) are end-point activities except where the value is expressed as xO.lO. In these cases, the end-point activity was not seen at the highest tested concentration. For purpose of calculation of the synergy index and for operational definition of MIC, the reported value could be an underestimate of the true MIC; thus the true synergy index could be even lower. 10 TABLE 1 Compound A = Prochloraz Compound B = Triadimefon end-point activity in ppm calculations ORGANISM QA QB Qa Qb Qa/Q Qb/Q SI A:B A B C versicolor 4 1 0.5 0.5 0.13 0.50 0.63 1:1 4 1 0.25 0.75 0.06 0.75 0.81 1:3 4 1 1.5 0.5 0.38 0.50 0.88 3:1 Tpalustris 128 2 1 1 0.01 0.50 0,51 1:1 128 2 6 2 0.05 1.00 LOO 3:1 Altemaria sp 1 128 1 1 1.00 0.01 1.01 1:1 1 128 1 3 LOO 0.02 1.02 1:3 1 128 0.75 0.25 0.75 0.00 0.75 3:1 Ophiostomci sp 1 8 0.5 0.5 0.50 0.06 0.56 1:1 1 8 0.25 0.75 0.25 0.09 0.34 1:3 1 8 0.75 0.25 0.75 0.03 0.78 3:1 Diplodia sp 1 32 0.5 0.50 0.50 0.02 0.52 1:1 ] 32 0.50 1.50 0.50 0.05 0.55 1:3 1 32 0.75 0.25 0.75 0.01 0,76 3:1 Penicillium sp 32 128 16 48 0.50 0.38 0.88 1:3 32 128 24 8 0.75 0.06 0.81 3:1 Synergistic ratios of compound A: compound B range from 3:1 to 1:3 TABLE 2 Compound A = Prochloraz Compound B = 2-n-octyl-3-isothiazalone end-point activity in ppm calculations ORGANISM QA QB Qa Qb Qa/Q Qb/Q SI A:B A B C versicolor 16 64 8 8 0.50 0.13 0.63 1:1 16 64 4 12 0.25 0.19 0.44 1:3 16 64 6 2 0.38 0.03 0.41 3:1 T palustris 64 64 32 32 0.50 0.50 LOO 1:1 64 64 16 48 0.25 0.75 1.00 1:3 Altemaria sp 2 16 1 3 0.50 0.19 0.69 1:3 2 16 1.5 0.5 0.75 0.03 0.78 3:1 Ophiostoma sp 1 4 0.25 0.75 0.25 0.19 0.44 1:3 1 4 0.75 0.25 0.75 0.06 0.81 3:1 Diplodia sp 2 4 0.5 1.50 0.25 0.38 0.63 1:3 2 4 0.75 0.25 0.38 0.06 0.44 3:1 Penicillium sp 32 32 16 16 0.50 0.50 1.00 LI 32 32 8 24 0.25 0.75 1.00 1:3 32 32 24 8 0.75 0.25 LOO 3:1 Synergistic ratios of compound A: compound B range from 3:1 to 1:3 SPEC) 118 24/08/99 11 TABLE 3 Compound A = Compound B = = Prochloraz Propiconazole end-point activity in ppm calculations ORGANISM QA QB Qa Qb Qa/Q A Qb/Q B SI A;B Tpalustris 128 32 48 16 0.38 0.50 0.88 3:1 Altemaria sp 128 16 24 8 0.19 0.50 0.69 3:1 Ophiostoma sp 128 4 4 4 0.03 LOO 1.03 1:1 128 4 6 2 0.05 0.50 0.55 3:1 Diplodia sp 1 4 0.5 0.50 0.50 0.13 0.63 1:1 1 4 0.25 0.75 0.25 0.19 0.44 1:3 1 4 0.75 0.25 0.75 0.06 0.81 3:1 Penicillium sp 128 4 4 4 0.03 1.00 1.03 1:1 128 4 6 2 0.05 0.50 0.55 3:1 Synergistic ratios of compound A; compound B range from 3:1 to 1:3 As can be seen by review of Tables 1-3, the compositions of the invention demonstrate synergistic microbiocidal activity as measured by minimum inhibitory concentrations (MIC) and show surprisingly greater activity than the algaebraic sum of the individual components which make up each composition. The synergistic activities of the compositions of the invention in most cases are applicable to fungi, especially wood destroying and wood staining fungi. Thus, the combinations not only lower the use level of biocide but also broaden the spectrum of activity. This is especially useful in situations where either component alone does not achieve the best results due to weak activity against certain organisms. SI'Lt'1118 24/08/99 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> WE CLAIM IS: 12 ft: - s ;- A microbiocidal composition including Prochloraz as a first component and a second component which includes either triadimefon, propiconazole or 2-n-octyl-3-isothiazalone, wherein the weight ratio of first component to second component is in the range of from substantially 32:1 to substantially 1:16. The composition according to claim 1 wherein the weight ratio of first compound to second compound is in the range of from substantially 32:1 to substantially 1:2. A microbiocidal product containing from substantially 5 to substantially 30% by weight of the composition as claimed in claim 1. The product as claimed in claim 3 incorporated into or onto a locus in the form of an aqueous medium, the composition being additionally contained in an emulsifier and water. A microbiocidal composition which comprises Prochloraz as a first component and a second component which comprises triadimefon, propiconazole or 2-n-octyl-3-isothiazalone as the secondary compounds, where in the weight ratio of the first • ItLLECTUAl PROPER IY urn., OF NZ 2 h AUG 2000 PFCEIVED 13 component to second component is in the range of from 2:1 to substantially 1:31. 6. The composition of claim 5 wherein the weight ratio of the first component to the second is in the range of from about 2:1 to about 1:2. 7 . A microbiocidal composition which comprises Prochloraz as a first component and a second component of which comprises triadimefon, propicanazole or 2-n-octyl-3-isothiazalone, wherein the weight ratio of first component to second component is in the range of from substantially 4:1 to substantially 1:16. 8. The composition as claimed in claim 7 wherein the weight ratio of first component to second component is in the range of from about 4:1 to about 1:1.25 and from substantially 5 to 30% of the composition. 9. A microbiocidal product containing a composition according to claim 1 with an emulsifier and water. 10. A microbiocidal product containing a composition according to claim 5 with an emulsifier and water. 11. A microbiocidal product containing a composition according to claim 7 with an emulsifier and water. SPEC HI 8 21/08/99 14 12. A method for inhibiting the growth of fungi, particularly wood destroying fungi or wood staining or moulding fungi in or on a locus subject to contamination by bacteria, fungi or algae which comprises incorporating onto or into the locus, an amount of the composition of claim 1 which is effective to effect adversely the growth of the fungi. 13. The method as claimed in claim 12 wherein the locus is an aqueous medium and the composition additionally contains an emulsifier and water. 14. A composition as claimed in any one of claims 1, 5 and 7 substantially as herein described with reference to the examples. 15. A method for inhibiting the growth of fungi using a composition as claimed in any one of claims 1, 5 and 7 substantially as herein described. PETER JAMES HAYWARD, GEORGE WILLIAM MASON, WALLACE J RAE, and JOHN DOYLE By their Attorney DON HOPKINS & ASSOCIATES ittLiijiUrtL PHUPBin ui t,.. OF NZ 2 4 AUG 2000 5PEC1118 RECEIVE 0 EZMQ </div>