AU736537B2 - Chemical composition and method of use - Google Patents

Description

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION STANDARD PATENT Applicant(s): WENDY LORRAINE MARSDEN Invention Title: CHEMICAL COMPOSITION AND METHOD OF USE The following statement is a full description of this invention, including the best method of performing it known to me/us: Ve.: .00.

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0 0*SS 1 CHEMICAL COMPOSITION AND METHOD OF USE The present invention relates generally to chemical preparations and compositions and to biocide treatments using such preparations and compositions, and particularly to biocide preparations and methods of using such preparations which selectively kill lower plant life. More particularly, the present invention relates to preparations or compositions and to methods of using such preparations and compositions to kill fungi and the like including mould, algae and liverwort and their spores. More particularly the present invention relates to preparations or compositions and to methods of using such preparations and compositions to kill spores and fungi of Phytophthora cinnamomi, (commonly known as cinnamon fungus). Even more particularly, the present invention relates to a new selective biocide preparation or composition suitable for use in selectively killing fungi and the like in cleaning operations, particularly in pour-on, dip, washdown or spray application to man made articles such as tools, clothing such as shoes or boots, vehicles including vehicle tyres, camping equipment such as tents and tarpaulins. The present invention further relates to a new selective phytophthora biocide preparation or composition suitable for pour-on, washdown or spray application to naturally occurring organic matter such as plants, seedlings, seeds, bulbs, soil, mulch and the like.

Although the present invention will be described with particular reference to a preparation or composition for pour-on, dip, washdown or spray application to an article or area affected by cinnamon fungus, it is to be noted that H: \Priyanka\Keep\speci \cinnamon.MARSDEN.doc 6/08/97 I I 2 the scope of the present invention is not so limited but rather the scope of the present invention is broader so as to include other preparations and compositions, other methods of manufacturing such preparations and compositions and other methods of using the preparations and compositions including other ways of administering the preparations or compositions than are specifically described in the present specification. The scope of the present invention is not limited to fungi but includes allied lower plants such as moulds and other cryptogamous plants without chlorophyll feeding on organic matter.

Many lower plants propagate and spread relatively easily by distribution of their spores or by regrowth or regeneration of parts of the plant. The distribution may be facilitated by the natural elements, particularly wind or water, or by animals including people. Spores and sometimes entire lower plants may be picked up on various articles such as vehicle tyres, shoes and tools, only to be removed or fall 20 off the article after the article has been transported a long distance from their origin. Commercial outlets for garden suppliers often inadvertently included spores and lower plants in their garden products such as mulch, soil, wood chips and higher plants. Purchasers transfer the lower plants and spores to wherever they utilise the garden products and higher plants.

Some fungi and the like live in synergy with their environs but others do not. For example, cinnamon fungus is a soilborne root pathogen known to cause dieback and death of susceptible plants, particularly members of the pine and eucalypt families. In many countries such as Australia, pines and eucalypts are very common in forests, plantations, farm and roadside shelterbelts, parks, nurseries and home gardens so that cinnamon fungus presents a threat to the survival of many trees. The spread of the cinnamon fungus is not only an ecological problem but an H:\Priyanka\Keep\speci\cinnonnMRSDFN.doc 6/08/97 3 economic problem which threatens the economy of several industries including the forest products industry and garden nursery industry.

Efforts have been made in the past to counter the spread of lower plants by the use of selective biocide preparations.

Commonly these selective biocide preparations comprise hypochlorite, chlorine derivatives, phenol or phenol derivatives and are used to washdown tools, vehicles and the like prior to their removal from infected areas in which the fungi grow.

In washdown applications, the selective biocide will be in contact with the article being washed down for only a few seconds or, at the longest, a few minutes. Therefore, optimally the selective biocide preparation will act rapidly to kill all the targeted lower plant species and their spores. However, the selective biocide preparations of the prior art and/or hitherto before used are often 20 ineffective at low concentrations and usually fail to kill the lower plants within a reasonable time or kill the plant, but not its spores.

For example, Noske and Shearer (Australian Plant Pathology (1985) 14:37-40) have shown that sodium hypochlorite at concentrations below 10% active ingredient is ineffective in suppressing growth of cinnamon fungus within a reasonable time. Similarly, the commercially available product BIOGRAM fails to inhibit cinnamon fungus growth 30 when the concentration of the phenol based active agent falls below (BIOGRAM is a trade mark) Noske and Shearer also showed that biocides comprising as little as 0.3% of one or more quaternary ammonium compounds as active ingredient can significantly suppress growth of cinnamon fungus. However, they were unable to find any significant difference between the efficacy of different quaternary ammonium compounds.

H:\Priyanka\eep\speci\cinnamon.MARSDNdoc 6/08/97 19/06 '01 TUE 14:06 FAX 61 3 9243 8333 GRIFFITH HACK [005 4 One of the other problems of the selective biocides of the prior art, typically not containing a quaternary ammonium species, is that their use is limited to washdown formulations, and they cannot be directly applied to higher plants such as trees because they will adversely affect the higher plant. Selective biocides of the prior art tend to kill juvenile trees or seedlings onto which they are sprayed. Furthermore, bulbs or seeds planted in soil treated with biocides of the prior art often will not develop and grow.

Therefore there is a need to provide a selective biocide preparation which can kill the majority of a given population of lower plants and spores within a reasonable 15 time at a reasonable concentration yet not poison soil or S* adversely affect higher plants, even when directly applied S: to the higher plants.

It is an aim of the present invention to provide a selective biocide preparation or composition for use in killing lower plants and spores which at least alleviates one or more of the problems of existing biocide treatments, and at least improves the killing or eradication of lower plants, particularly fungi, algae, mould or liverwort and more particularly cinnamon fungus.

According to the present invention there is provided a selective biocide preparation or composition capable of killing lower plants and spores, said preparation or composition including in combination from 0.01 to 80% by weight of a benzalkonium compound and from 0.01 to 50% by weight of an ameliorating agent being phosphate or a phosphate-containing material.

Typically said composition will comprise in combination a quaternary ammonium compound, an ameliorating agent, a solvent and a surfactant.

\\BmelbK6lc\homec lrkelc.IlRecyte 3215-17 wndy Lorri mrden,.doo 1/O/l 19/06 '01 TUE 14:06 [TX/RX NO 5067] 5 According to another aspect of the present invention there is provided a method of treatment at a locus comprising administering or applying a selective biocide preparation or composition to a locus which is in contact with lower plants and/or spores in which the preparation or composition comprises in combination a quaternary ammonium compound and an ameliorating agent for aiding transport of the quaternary ammonium compound across plant cell walls.

Typically said method of treatment at a locus comprising administering or applying a selective biocide preparation or composition to a locus which is in contact with lower plants and/or spores in which the preparation or composition comprises in combination a quaternary ammonium compound, an ameliorating agent, a surfactant and a solvent.

According to another aspect of the present invention there is provided a method of treatment of a man made article or naturally occurring material comprising administering or applying a selective biocide preparation or composition to a man made article or naturally occurring material carrying *lower plants and/or spores in which the preparation or I%%composition comprises in combination a quaternary ammonium compound and an ameliorating agent. Typically said method of treatment of naturally occurring material comprising administering or applying a selective biocide preparation or composition to a naturally occurring material carrying lower plants and/or spores in which the preparation or composition comprises in combination a quaternary ammonium compound, an ameliorating agent, a surfactant and a solvent.

According to another aspect of the present invention there is provided a method of treatment by killing lower plants and or spores to enhance an environment comprising administering or applying a selective biocide preparation H:\Priyanka\Keep\speci\ci nn ofon.MARSDEN.doc 6/08/97 6 or composition to the environment contaminated with lower plants and/or spores in which the preparation or composition comprises in combination a quaternary ammonium compound and an ameliorating agent.

According to another aspect of the present invention there is provided a method of making a selective biocide preparation or composition comprising in combination a quaternary ammonium compound and an ameliorating agent said method comprising the step of mixing in combination a quaternary ammonium compound and an ameliorating agent for aiding transport of the quaternary ammonium compound across plant cell walls. Typically said method of making a selective biocide preparation or composition comprises mixing in combination a quaternary ammonium compound, an ameliorating agent, a surfactant and a solvent.

Typically the lower plant is a fungus, algae, mould or liverwort or spores thereof. More typically the lower 20 plant is a fungus or mould. More typically the lower plant is a phytophthora fungi, particularly cinnamon fungus.

Typically the composition of the present invention can be applied or administered in a number of suitable ways, such as for example as a spray, dip, drench, pour-on or washdown. The method of application or administration will vary depending on the conformation of the man made article or natural organic matter to which the composition is to be applied. For example, the composition is probably most conveniently applied to plants by spraying and to vehicles by washdown formulation.

Typically where man made articles are to be treated with the selective biocide of the present invention, the selective biocide will be applied by washdown of the man made article. Typically where boots, shoes and other foot coverings or vehicle tyres are to be treated, the foot H:\Priyanka\Keep\speci\cinnamon.MARSDEN.doc 6/08/97 '6 7 coverings or vehicle tyres will be walked or driven respectively, through a trough or other receptacle containing the selective biocide. Typically, the locus includes implements, tools, equipment or the like, or plant matter.

Typically the quaternary ammonium compound is a benzalkonium compound. More typically the quaternary ammonium compound is a benzalkonium halide. Even more typically the quaternary ammonium compound is chosen from the group comprising alkyldimethylbenzylammonium halide, alkylmethylethylbenzylammonium halide and alkyldiethylbenzylammonium halide where the halide is chosen from the group comprising chloride, bromide or iodide and the alkyl moiety is chosen from the group comprising Ci to C 40 alkyl chains. Typically the alkyl moiety is chosen from the group comprising C 1

C

30 alkyl chains, more typically C 1

C

20 alkyl chains preferably

C

12

C

16 Even more typically the quaternary ammonium 20 compound is alkyldimethylbenzylammonium chloride such as QUATRAMINE 50 from APS Chemicals formerly Harcros Industrial Chemicals. (QUATRAMINE is a trade mark.) Commercially, quaternary ammonium compounds are often supplied as mixtures of quaternary ammonium compounds having alkyl chains of various carbon chain lengths. For example QUATRAMINE'50 is a 50% active solution of alkyldimethylbenzylammonium chloride (also known as coco dimethylbenzylammonium chloride). The typical alkyl chain length distribution of QUATRAMINE 50 is C 12 63% C 14 30% 3% and 7% 2%.

Typically the ameliorating agent is a phosphate. More typically the ameliorating agent is a tri-polyphosphate.

Even more typically the ameliorating agent is chosen from the group comprising sodium tri-polyphosphate or potassium tri-polyphosphate. The ameliorating agent in combination with the quaternary ammonium compound of the present H:\Priyanka\Keep\speci\ci nnfon. MARSDEN.doc 6/08/97 8 invention provides a preparation or composition which is of significantly greater effect as a biocide than analogous compositions comprising a quaternary ammonium compound in the absence of the ameliorating agent. Without wishing to be bound by theory, it is believed that the ameliorating agent acts synergistically with the quaternary ammonium compound to increase the biocidal activity of the quaternary ammonium compound. Again without wishing to be bound by theory, it is believed that the ameliorating agent aids the transport of the quaternary ammonium compound across plant cell walls.

Typically the surfactant is a nonyl phenol derivative, alkylpolysaccharide derivative or the like. More typically o. 15 the surfactant is chosen from the nonyl phenol derivatives known commercially by the trade mark TERIC. (TERIC is a trade mark.) More typically the surfactant is chosen from the nonyl phenol derivatives known as TERIC GN series surfactants. Even more typically the surfactant is TERIC.

20 GN-9 surfactant.

Typically the solvent may be chosen from any of the solvents well known in the art to be suitable for selective biocide preparations or compositions of the present type.

25 More typically the solvent is a polar solvent. Even more typically the solvent is chosen from the group comprising water or alcohol.

Typically the selective biocide preparation or composition of the present invention comprises between 0.01 and 80.00 wt active ingredient quaternary ammonium compound.

More typically the selective biocide preparation or.

composition comprises between 0.10 and 5.0.00 wt a.i.

quaternary ammonium compound. Even more typically the biocide preparation or composition comprises between 5.00 and 25.00 wt a.i. quaternary ammonium compound.

\\melbf i es\home$\bourke\Keep\Speci\ci cao& J. MARSDEN. doc 14/05/01 9 Typically the selective biocide preparation or composition of the present invention comprises between 0.01 and 50.00 wt of ameliorating agent for transport of the quaternary ammonium compound across plant cell walls. More typically the selective biocide preparation or composition comprises between 0.10 and 5.00 wt ameliorating agent. Even more typically the biocide preparation or composition comprises between 1 and 4 wt ameliorating agent.

Typically the selective biocide preparation or composition of the present invention comprises between 0.01 and 50.00 wt surfactant. More typically the selective biocide preparation or composition comprises between 0.10 and 5.00 wt surfactant. Even more typically the biocide preparation or composition comprises between 1 and 4 wt surfactant.

I Typically the selective biocide preparation or composition of the present invention comprises between 10 and 90 wt 20 solvent. More typically the selective biocide preparation or composition comprises between 20 and 80 wt solvent.

Even more typically the biocide preparation or composition comprises.between 60 and 80 wt solvent.

In a particularly preferred embodiment the biocide preparation or composition of the present invention comprises the following formulation; sodium tripolyphosphate 2 3 wt% TERIC GN-9 surfactant 7 8 wt% alkyldimethylbenzylammonium chloride9 11 wt% water balance Typically the quaternary ammonium compound and ameliorating agent for transport of the quaternary ammonium compound across plant cell walls are mixed with any other suitable, H: \Priyanka\Keep\peci\cinn .MAsDE.doc 6/08/97 10 convenient or desirable components to form a suitable composition, such as a foam suppressant agent, colorant, emetic or the like.

The composition can take any suitable form such as a solution or emulsion including macro-emulsion or microemulsion. However, it is to be noted that the method of application or administration of the composition is dependent on the dosage and concentration of the active components in the composition so that undesirable effects of the composition are taken into account such as for example the toxicity of any of the components to some higher plants in some concentrations and/or dosages. The method of application and/or administration is determined so as to be efficient and efficacious without being harmful.

1 The present invention will now be described by way of 20 example with reference to the following examples; Example 1 Comparison of quaternary ammonium compounds in inhibiting cinnamon fungus Cinnamon fungus (CFTT isolate No. 41) was grown on autoclaved potato dextrose agar (PDA) in petri dishes at 0 C for 4 days. From the edge of the cultures, a 6.5 mm diameter plug of agar was cut and placed in the centre of 2 lines (x y) drawn at right angles on 40 plates of PDA amended with three selective biocide compositions at 0.07 wt a.i. and a control that contained no additives plates per treatment). The three selective biocide compositions and their active ingredients are listed in Table 1. The plates were incubated at 25 0 C and the colony diameter growth along each line was measured at the same time each day at 1, 2, 3, 4, 7, 8 and 9 days after plating and the average linear diameter growth of the culture H: \Priyanka\Keep\speci\cinnamon .MARSDEN.doc 6/08/97 11 r.

a.

p recorded using: Average colony diameter diameter x y of colony agar plug diameter of plug 2 Final colony diameter was analysed using analysis of variance. Survival of the plugs where no growth-occurred was assessed by plating on PDA agar after 10 days.

Table 1.

Biocide Active Ingredient ABF42 10/g/l Poly [Oxyethylene (Dimethyliminio) Ethylene Dichloride] Chemene 128 g/l Benzalkonium chloride Test 1 128 g/l Benzalkonium chloride sodium triphosphate ABF42 and Chemene are commercially available selective biocides comprising quaternary ammonium compounds as active ingredients. The selective biocide identified as Test 1 comprises a quaternary ammonium compound and tripolyphosphate as ameliorating agent according to the present invention.

ABF42 reduced the cinnamon fungus growth on the agar by 57 Conversely, Chemene Test 1 completely suppressed the growth of the cinnamon fungus on the agar. The growth of the cinnamon fungus plated on PDA agar amended with 0.07 wt% active ingredient of ABF42, Chemene and Test 1 is recorded graphically in Figure 1. Comparison of the growth suppression caused by ABF42, Chemene and Test 1 with the control plates shows the clear superiority of Chemene and Test 1 over ABF42.

After 10 days, the control plates and plates treated with H: \Piiyanka\Keep\speci\cinnamon .MARSENdoc 6/08/97 12 ABF42 and Chemene showed 100 survival of the cinnamon fungus. Conversely the Test 1 formulation completely suppressed cinnamon fungus growth on plates. Results are recorded in Table 2.

Table 2.

Biocide Survival ABF42 100 Chemene 100 Test 1 0 Control 100 Example 2 Comparison of different concentrations of quaternary ammonium compounds in inhibiting cinnamon fungus Cinnamon fungus (CFTT isolate No. 41) was grown and transferred to petri dishes as for Example 1 but on 160 lates of PDA amended with the three selective biocides on Table 1 at 0.2, 0.1, 0.05, 0.025, and 0.0125 wt a.i. and a control that contained no additives (10 plates per 15 treatment). The plates were incubated for 1, 2, 3, 4 7 S* days and measured as for Example 1. Survival of the plugs was assessed after 7 days.

Test 1 at all rates tested gave complete suppression of the pathogen. Chemene also completely suppressed growth down to 0.025 wt a.i. with some growth at 0.0125 wt a.i.

The growth of the cinnamon fungus plated on PDA agar amended with 0.2, 0.1, 0.05, 0.025 and 0.0125 wt% active ingredient of ABF42, Chemene and Test 1 is shown graphically in Figure 2. Figure 2 shows that ABF42 reduced growth by 75% at 0.1 wt a.i. and at 0.2 wt a.i. growth was completely suppressed. Test 1, Chemene and ABF42 at 0.2 wt a.i. also caused complete mortality of the fungus after ten days on the plate although Chemene and ABF42 did not reduce survival below this level. The Test 1 H:\Priyanka\Keep\speci\cinnamon.MARSDEN.doc 6/08/97 13 composition effectively killed the fungus down to 0.025 wt %6 a.i.

Table 3 records survival rate of the cinnamon fungus 7 days after planting on PDA agar amended with 0.2, 0.1, 0.05, 0.025 and 0.0125 and wt %6 a.i. of ABF42, Chemene and Test 1.

Table 3.

Biocide Concentration Survival ABF42 0.2 0 0.1 100 0.05 100 0 .025 100 0.0125 100 Chemene 0.2 0 0.1 100 0.05 100 0.025 100 __0.0125 100 Test 1 0.20 0.1 0 0.05 0 0.025 0 0.0125 100 Control 0 100 p

I.

Example 3 Comparison of Cheuene Test 1 Cinnamon fungus (CFTT isolate No. 4) was grown and transferred to petri dishes as for Example 1. 49 plates of PDA were amended with Chemene and Test 1 at 0.025, 0.0125 H \Priyanka\Keep\speci\cinnl~onl ARSDENdoc 6/08/97 14 and 0.00625 wt a.i. and the rest were treated with a control that contained no additives (7 plates per treatment). The plates were incubated for 1, 4 11 days and measured as for Example 1.

In this experiment, Test 1 again completely suppressed the cinnamon fungus at all rates tested. Chemene also completely suppressed growth down to 0.0125 wt a.i. with some growth at ).00625 wt a.i. after 11 days.

Figure 3 graphically records the growth of the cinnamon fungus plated on PDA agar amended with 0.025, 0.0125 and 0.0625 wt% of Chemene and Test 1.

Example 4 Comparison of quaternary ammonium compounds in inhibiting cinnamon fungus in plant material The ability of quaternary ammonium compounds to kill cinnamon fungus in plant material was assessed using 20 infected Eucalyptus sieberi cotyledons. Cotyledons were floated in naturally infested soil for 4 days and following infection 30 were dipped in each of the following treatments: distilled water (ii) ABF42 at 1.0, 0.2 and 0.05 wt for second, 5 minutes and 10 minutes (iii) Chemene at 1.0, 0.2 and 0.05 wt a.i.

for 30 seconds, 5 minutes and minutes (iv) Test 1 at 1.0, 0.2 and 0.05 wt a.i.

for 30 seconds, 5 minutes and minutes After dipping, the cotyledons were washed in distilled water and plated onto PDA agar and survival assessed through growth on the agar.

H: \PriYanka\Keep\seci\cinnon .MARSDEN.doc 6/08/97 15 Resolution of the fungus from all treatments showed that no disinfectant at any rate or time tested was able to kill the fungus within the infected cotyledon. The disinfectants in fact provided a good surface sterilant of the cotyledon in that few contaminants were found growing on the agar after plating.

Example 5 Comparison of quaternary ammonium compounds in inhibiting cinnamon fungus in soil The ability of quaternary ammonium compounds to kill cinnamon fungus in soil was assessed by baiting soil treated with Test 1. Infested soil (100 g) was placed in cloth bags and soaked in Test 1 at 1.0. 0.2 and 0.05 wt a.i. for 30 seconds, 5 minutes and 10 minutes. The soil wa then washed 3 times in distilled water following the initial treatment, allowed to drain and then 50, 25, 12.5, 6.25, 3.12, 1.56, 0.78, 0.39, 0.19 and 0.098 g of treated soil were weighed into 100 ml plastic cups and flooded with distilled water. Eucalyptus sieberi cotyledons were floated on the surface of the water and after 4 days were assessed for the presence of cinnamon fungus using sporangial characteristics.

Figure 4 records the number of infective propagules of cinnamon fungus per gram of soil treated with Test 1 at 0.2 and 0.05 wt% active ingredient for 30 seconds, minutes and 10 mintes. Figure 4 shows that Test 1 at 0.2 wt a.i. significantly reduced the amount of infective propagules of P. cinnamomi present in the soil. At 1.0 wt no fungus could be isolated. Time of immersion appeared to have little effect on isolation of the fungus.

H :\Priyanka\Keep\speci\cjnnaon.MARSDEN.doc 6/08/97 16 Example 6 Inhibition by Test 1 of cinnamon fungus zoospore infection of plants from soil The ability of Test 1 to inhibit cinnamon fungus zoospore infection of plants from soil was assessed by treating infested soil with the disinfectant. Infested soil (30 g) was placed in 100 x 100 ml plastic cups and flooded with a 0.1, 0.01 wt a.i. solution of Test 1 and distilled water (10 cups per treatment). Eucalyptus sieberi cotyledons were floated on the surface of the water and after 4 days were assessed for the presence of cinnamon fungus using sporangial characteristics or, in the absence of sporangia, plating on PDA agar.

Table 4 records the degree of infection of Eucalyptus sieberi cotyledons by zoospores of cinnamon fungus 4 days after treating soil flooded with 1.0, 0.1, 0.01, 0.001 wt a.i. of Test 1.

20 Table 4.

Biocide Concentration a.i. Cotyledon infection Test 1 1.0 0 0.1 0 0.01 0 0.001 100 Control 0 100 Test 1 at rates down to 0.01 wt a.i. prevented zoospore infection of the cotyledon over the 4 days that the test ran. At 0.001 wt a.i. however, it was ineffective with all cotyledons examined showing sporangia around the edge of the treated soil.

H:\Priyanka\Keep\speci\cinnamon. MARSDEN.doc 6/08/97 17 Example 7 Testing of the phytotoxicity of Test 1 The phytotoxicity of a 1 wt solution Test 1 was tested on nine, 18 month old (8 months in 3 litre pots) Pinus radiata seedlings grown in a glasshouse maintained at 22 0

C.

Seedlings were subjected to the following treatments (three per treatment).

1. 300 ml of 1 wt a.i Test 1 applied as a soil drench to each pot. The plants were allowed to sit in trays until all the disinfectant was absorbed. The plants were then rewatered.

2. Test 1 at 1 wt a.i applied as a foliage spray until drip point.

3. Control. Distilled water applied as above without the disinfectant.

20 Table 5 records the results of phytotoxicity testing of a 1 wt a.i solution of Test 1 to Pinus radiata seedlings when applied as a soil drench and a foliage spray.

Some degree of phototoxicity was shown when a 1 wt a.i solution of Test 1 was applied to the foliage of P. radiata seedlings. No phytotoxicity was observed when applied as a drench. No mortality was observed.

H: \Priyanka\Keep\speci\cinnaon .MARSDEN.doc 6/08/97 18 Table Treatment Replicate Foliage Health Soil Drench 1 Healthy green 2 Healthy green 3 Healthy green Foliage Spray 1 Some browning 2 Slight browning 3 Slight browning Control 1 Healthy green 2 Healthy green 3 Healthy green In summary, Examples 1 to 7 show that Test 1 (a combination of benzalkonium chloride and sodium tri-phosphate) had a greater efficiency in killing and inhibiting the growth of *I cinnamon fungus than Chemene (Benzalkonium chloride alone) or ABF42 (poly [oxyethylene (dimethylimino)] ethylene dichloride.

Test 1 was effective at rates as low as 0.01 wt a.i in preventing zoospore infection in soil and killed the fungus on agar at rates as low as 0.025 wt No trace of the fungus could be isolated from soil drenched in a 1 wt a.i solution for 30 seconds and the chemical dramatically reduced levels of infective propagules at 0.2 wt a.i. No phytotoxicity was observed when Test 1 at 1 wt a.i was applied as a soil drench to potted P. radiata seedlings,

V.

although some needle browning was observed when applied as a foliage spray.

ABF42 was effective at rates of 0.2 wt a.i in killing the fungus on agar but although reducing fungal growth at 0.1 wt a.i was completely ineffective below these rates.

Chemene was also effective at 0.2 wt a.i in killing the fungus on agar and inhibited growth at all rates tested.

H \Priyanka\Keep\speci\cinnamonmRSDE doc 6/08/97 However, below 0.2 wt a.i it was ineffective in killing the fungus. None of the disinfectants were able to kill the fungus within host tissue within the times tested (up to 10 minutes of immersion).

Advantages of the present invention include the following: 1) The composition is inexpensive to manufacture; 2) There are no or minimal side effects to the environment other than lower plants; 3) There are no serious drawbacks or disadvantages with long term use of the compositions; 4) The composition can be readily made without the need to use expensive equipment; 15 5) The composition is quick-acting and improvements are noted shortly after use is commenced.

The described arrangement has been advanced by explanation and many modifications may be made without departing from the spirit and scope of the invention which includes every novel feature and novel combination of features herein disclosed.

Those skilled in the art will appreciate that the invention 25 described herein is susceptible to variations and modifications other than those specifically described. It is understood tha the invention includes all such variations and modifications which fall within the spirit.

and scope.

For the purposes of this specification it will be clearly understood that the word "comprising" means "including but not limited to", and that the words "comprise" and "comprises" have a corresponding meaning.

AN H: \mbourke\Keep\Speci\cinam on.MARSDEN.doc 14/05/01

CL

l3 0

Claims (26)

1. A selective biocide preparation or composition for killing lower plants and spores, said preparation or composition including in combination from 0.01 to 80% by weight of a benzalkonium compound and from 0.01 to 50% by weight of an ameliorating agent being phosphate or phosphate-containing material.

2. A selective biocide preparation or composition according to claim 1 which further includes a solvent and a surfactant.

3. A selective biocide preparation or composition according to claim 1 or 2 wherein the benzalkonium compound is a benzalkonium halide.

4. A selective biocide preparation or composition according to claim 1 or 2-wherein the benzalkonium compound is aJlkyldimethylbenzylamlonium halide, alkylmethylethylbenzylammonium, hal ide or alkyldiethylbenzylamonium halide.

S. A selective biocide preparation or composition according to claim 3 or 4 wherein the halide is a chloride, bromide or iodide and the alkyl moiety is a Cl to C40 alkyl chain.

6. A selective biocide preparation or composition according to claim 5 wherein the alkyl. moiety is a Cl to alkyl chain.

7. A selective biocide preparation or composition according to claim 6 wherein the alkyl moiety is a C12-to C16 alkyl chain. \\l-ic~emgPlrL\~pRt~~3259 IAkylrricm win0c10DS9 19/06 '01 TUE 14:06 [TX/RX NO 5067] 19/06 '01 TUE 14:06 FAX 61 3 9243 8333 GRIFFITH HACK [Z007 -21.

8. A selective biocide preparation or composition according to any one of the preceding claims wherein the ameliorating agent is a phosphate.

9. A selective biocide preparation or composition according to claim 8 wherein the ameliorating agent is a trn-phosphate.

A selective biocide preparation or composition according to claim 8 or 9 wherein the ameliorating agent is sodium tri-polyphosphate or potassium tri- polyphosphate.

11. A selective biocide preparation or composition according to any one of claims 2 to 10 wherein the surfactant is a noznyl phenol derivative or an alkylpolysaccharide derivative or mixtures thereof.

12. A selective biocide preparation or composition according to any one of the preceding claims including between 5.00 and 25.00 wt% benzalkonium compound.

13. A selective biocide preparation or composition according to any one of the preceding claims including between 9 and 11 wta alkyldimethylbeuZylamfonium chloride, and between 2 and 3 wts sodium tri -polyphosphate

14. A selective biocide preparation or composition according to any one of the preceding claims further including foam suppressant agents, colourants, emetics or mixtures thereof.

A selective biocide preparation'or composition according to any one of the preceding claims which is in the form of a solution or a macro-emulsion or a micro- emulsion. 19/06 '01 TUE 14:06 [TX/RX NO 5067]

16. A method of treatment at a locus including administering or applying a selective biocide preparation or composition according to any one of the preceding claims to a locus which is in contact with lower plants and/or spores.

17. A method of treatment of a man made article or naturally occurring material including administering or applying a selective biocide preparation or composition according to any one of claims 1 to 15 to the man made article or naturally occurring material carrying lower plants and/or spores.

18. A method of treatment by killing lower plants and/or spores to enhance an environment including administering or applying a selective biocide preparation or composition according to any one of claims 1 to 15 to the environment contaminated with lower plants and/or spores. 20

19. A method of treatment according to any one of claims 16 to 18 wherein the lower plants are fungi, algae, moulds or liverworts and the spores are derived therefrom.

A method of treatment according to any one of claims 25 16 to 18 wherein the lower plants are phytophthora fungi and the spores are derived from phytophthora fungi.

21. A method of treatment according to any one of claims 16 to 18 wherein the lower plant is cinnamon fungus and the spores are derived from cinnamon fungi.

22. A method of treatment according to any one of claims 16 to 21 wherein the selective biocide preparation or composition is administered or applied by pour-on, dip, wash-down or spray methods. H: \mbourke\Keep\Speci\cinnm on.MARSDEN.doc 14/05/01 19/06 '01 TUTE 14:07 FAX 61 3 9243 8333 GIFT AKLjo GRIFFITH RACK a 008

23- 23. A method of making a selective biocide preparation or composition of any one of claims 1 to 16 including the Btep of mixing in combination the benzalkonium compound and the ameliorating agent.

24. A selective biocide preparation or composition substantially as hereinbefore described with reference to the foregoing examples.

25. A method of treatment using a selective biocide prep~aration or composition substantially as hereinbefore described with reference to the foregoing examples.

26. A Method of making a selective biocide preparation or composition substantially as hereizzbefore described with reference to the foregoing examples. Dated this 18th day of June 2001 WENDY LORPXNE NMRSDEB By their Patent Attorneys GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia 19/06 '01 TUE 14:06 [TX/RX NO 5067]