AU2016101508A4 - Fungicide composition and method - Google Patents

Abstract

An aqueous flutriafol suspension concentrate composition comprising: (a) flutriafol in an amount of at least 550g/L of concentrate composition; (b) water in an amount of less than about 400 g/L of concentrate composition; and (c) a surface active agent composition comprising at least one selected from the from the group consisting of (i) comb-graft copolymers wherein the graft component comprises polyethylene oxide moieties and the backbone component comprises (in polymerised form) acylic or methacylic acids or salts or esters thereof (ii) linear copolymers of an oily monomer and an acrylic or methacylic or maleic acid monomer, or anionic salts thereof and (iii) alcohol ethoxylates. STRIPE RUST % tillers infected 104 DAS -e 150 (D 1 2 3 4 5 6 7 8 9 Figure 1

Description

Fungicide Composition and Method

Field [0001] This invention relates to suspension concentrates that comprise the fungicide flutriafol. In particular this invention relates to concentrated aqueous suspensions of the fungicide flutriafol.

Background [0002] Suspension concentrates (SC) comprise a mixture of finely milled insoluble active ingredient(s) and a surfactant system in water or an aqueous environment. When diluted with water, the formulation forms a fine dispersion that may be milky in appearance. Suspension concentrates should be (i) chemically stable, (ii) physically stable, especially with respect to settling out, floating out and rheological behaviour, (iii) easily poured and dispersed, and (iv) moderately stable in dispersed form after dilution, so that uniform material can be delivered from the spray tank at the point of use.

[0003] Flutriafol is a contact and systemic triazole fungicide that has protectant and eradicant action. It is a group 3 fungicide and provides inhibition of hyphal growth in fungi, and controls a broad spectrum of plant diseases caused by fungi.

[0004] Flutriafol has frequently been used as a component in seed dressing formulations and in this and other agricultural applications, the use of suspension concentrate formulations is advantageous because relatively high levels of active agent can be provided in a dust-free liquid form that can be delivered through a spray application.

[0005] Flutriafol suspension concentrates comprising 50% w/v of flutriafol active agent have been sold by a number of companies including Imtrade (as Flutriafol 500 SC) in Australia, Syngenta Crop Protection in North Ryde Australia (as Verge 500 SC), Apparent Pty Ltd in Australia (as Flutriafol 500 SC). FMC and Titan Ag sell similar products in Australia.

[0006] There is an ongoing need to develop liquid formulations of flutriafol that contain a greater loading of the active agent flutriafol. Formulations with higher loadings of active agent (but with equivalent bioactivity per unit weight of active agent) are important because (i) there is a reduction in transport and packaging costs (per unit quantity of active agent), (ii) there is a reduction in weight of product that needs to be carried by a worker in the agricultural industry, (iii) there is a reduction in the quantity of contaminated packaging that needs to be disposed of and (iii) there is a capacity for the manufacturer to demonstrate a higher level of formulation expertise to product users.

Summary [0007] There is provided an aqueous flutriafol suspension concentrate composition comprising: (a) flutriafol in an amount of at least 550g/L of concentrate composition; (b) water in an amount of less than about 400 g/L of concentrate composition; and (c) a surface active agent composition comprising at least one (preferably at least two and more preferably at least three) surface active agents selected from the from the group consisting of (i) comb-graft copolymers wherein the graft component substantially comprises polyethylene oxide moieties and the backbone component substantially comprises (in polymerised form) acylic or methacylic acids or salts or esters thereof; (ii) linear copolymers of an oily monomer and an acrylic or methacylic or maleic acid monomer, or anionic salts thereof and (iii) alcohol ethoxylates such as C12 - Cm alcohol ethoxylates or blends thereof.

[0008] In one set of embodiments there is provided a method of preventing or controlling fungal infestation in plants comprising applying to the site at which infestation is to be prevented or controlled the above described concentrate composition, optionally diluted with water prior to applying.

[0009] The first of the above surface active agents (c)(i) will be referred to as the comb-graft surfactant, the second of the surface active agents (c)(ii) will be referred to as the polycarboxylate surfactant, and the third of the surface active agents (c)(iii) will be referred to as the alcohol ethoxylate surfactant.

[0010] Throughout the description and claims of the specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

Detailed Description [0011] The combination of components and in particular with one or more of the surfactants, especially surfactants from two or three of the groups comb-graft surfactant, polycarboxylate surfactant, and alcohol ethoxylate surfactant, provide higher concentrations while maintaining stability of the suspension concentrate. More preferably three of the surfactant groups together allow particularly high concentrations to be realised while maintaining a stable composition.

[0012] Comb-graft polymers may comprise an acrylic acid, methacrylic acid, acrylate, methacrylate or methyl methacrylate polymer backbone and hydrophilic polyethylene glycol (PEG) branches extending from this backbone. The comb-graft copolymers used in the present invention are proprietary materials. Suitable comb-graft copolymers include, but are not limited to Tersperse® 2500 (about a 35% graft copolymer solution from Huntsman), Atlox® 4913 (about a 35% graft copolymer from Croda Uniqema), Ethacryl P® (a 35-45% graft copolymer solution from Lyondell Chemical Co.).

[0013] The group of polycarboxylate surfactants include copolymer of styrene and Na methacrylate (such as Tersperse 2700® available from Huntsman) and copolymer of isobutylene and maleic acid Na salt (such as Gerapon T/36 available from Rhodia).

[0014] Specific examples of alcohol ethoxylates such as Ci2 - Cu alcohol ethoxylates or blends thereof include Terperse®4894 (sold by Huntsman).

[0015] In one set of embodiments the composition comprises alcohol ethoxylate surfactant in an amount of froml 5-120 g/L (preferably from about 30 to 60 g/L and most preferably about 41 g/L) of the concentrate composition.

[0016] In one set of embodiments the concentrate composition comprises comb-graft surfactant in an amount of from 10-70 g/L (preferably 15 to 40 g/L and most preferably about 28 g/L) of concentrate composition.

[0017] In one set of embodiments the concentrate composition comprises polycarboxylate family surfactants in an amount of from 3-25 g/L (preferably from 5 to 15 g/L and most preferably about 8g/L) of the concentrate composition.

There may be one, two or three of the classes of surfactants referred to above.

[0018] The concentrate composition may comprise other formulation additives such as anti-foam agents (such as silicone anti-foam agents such as “Gensil 2030”), antimicrobial agents (such as benzisothiazolones such as “Acticide BW20”), thickening agents (such as gums, such as xantham gum such as “Rhodapol 50 MC”), pigment (such as red pigment such as “Novotex Red ARCY-BR”).

[0019] In one set of embodiments the weight ratio of flutriafol active agent to water is greater than 1.2/1, preferably greater than 1.4/1, more preferably greater than 1.6/1.

[0020] In one set of embodiments the alcohol ethoxylate surfactant is a C12 - Cu alcohol ethoxylate or ethoxylate blend comprising C12 - Cu alcohol ethoxylate.

[0021] In one set of embodiments the comb-graft family comprises a copolymer of acrylic and/or methacrylic acid (backbone) with methacrylic acid esterified with polyethylene oxide (graft) wherein the acrylic or methacrylic acid moieties are in salt form (such as sodium salt form).

[0022] The invention will now be described with reference to the following examples.

It is to be understood that the examples are provided by way of illustration of the invention and that they are in no way limiting to the scope of the invention.

EXAMPLES

Brief Description of Drawings [0023] The Examples are described in part with reference to the attached drawings.

[0024] In the drawings:

Figure 1 is a column chart showing the percent tillers infected 104 days after sowing for a number of treatments referred to in Trial 1.

Figure 2 is a column chart showing the percent tillers infected with stripe rist 118 days after sowing in accordance with the results in Table 10.

[0025] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.1.

Table 1.1 The composition of a Flutriafol (600 g/L)

[0026] In this and subsequent formulations of the invention (see Tables 1.2 to 1.7) the concentration (gram per litre) of dispersants is based on the weight of the active dispersant (excluding any solvent content in the commercial formulation of the dispersant).

[0027] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.2.

Table 1.2 The composition of a Flutriafol (600 g/L)

[0028] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.3.

Table 1.3 The composition of a Flutriafol (600 g/L)

[0029] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.4.

Table 1.4 The composition of a Flutriafol (600 g/L)

[0030] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.5.

Table 1.5 The composition of a Flutriafol (600 g/L)

[0031] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.6.

Table 1.6 The composition of a Flutriafol (600 g/L)

[0032] A flutriafol concentrate composition may be prepared comprising the following components in the amounts as specified in Table 1.7.

Table 1.7 The composition of a Flutriafol (600 g/L)

[0033] Formulation Process & Quality Control [0034] A 5L batch of a concentrate composition having the concentration of components shown in Table 1.7 was prepared in a pilot plant using the following manufacturing process.

[0035] Manufacturing Process

[0036] A typical manufacturing batch size would be 1,000L

Step 1: PREPARE THE MILL BASE BLEND 1.1 To a 1200 Litre stainless steel vessel, containing a paddle stirrer and variable speed mixer, charge glycerol (80% of total amount needed), Geropon T/36, Atlox 4894, Atlox 4913, Gensil 2030,

Acticide BW 20, Veegum T, and approximately 75% of the water required. Ensure the stirrer is on during additions. 1.2 Mix until homogeneous. 1.3 Turn on variable speed mixer and gradually add Flutriafol technical material to the vessel. Continue mixing until the technical material is uniformly dispersed and the mill base is free of any large lumps of powder. Once the powder has dispersed turn off variable speed mixer.

Step 2: MILL THE MILL BASE BLEND 2.1 Connect the vessel to the mill and ensure that the paddle stirrer in the tank is turned on to prevent the active ingredient from settling in the tank during the milling process. 2.2 Pass the mill base through a suitable bead mill (such as a Dyno-mill) to achieve a particle size distribution with 90% of particles less than 10 pm and 50% of particles less than 5 pm. Collect the mill base in a 1200 Litre stainless steel vessel. 2.3 Flush mill with rinse water (approximately 5% of the water required) once milling is complete.

Step 3: THICKEN THE BATCH 3.1 Prepare a premix in a 30 L pail by adding the remaining 20% of glycerol and the rhodapol 50 MC. Mix this with a paint stirrer to form a uniform dispersion. Ensure that there are no lumps in this pre-mix. 3.2 While mixing add the remaining 20% of water to the milled blend in the vessel. 3.3 Add the Novotex Red pigment to the vessel and continue to mix for approximately 30 minutes or until all the pigment lumps have broken up and dispersed to produce a uniform red liquid suspension. 3.4 Add the premix prepared in step 3.1 to the vessel and continue to mix for approximately 30 minutes. Avoid aeration during this step as it is difficult to de-aerate the suspension following the thickening stage. 3.5 Take a sample of the finished blend and submit to the laboratory for QC analysis.

[0037] Quality control [0038] Particle size [0039] A sample should be taken prior to the completion of Step 2.2 and analysed for particle size. If the particles are not within specifications it may be necessary to remill this batch and to reset milling flow rates in subsequent batches.

[0040] Active ingredient left in vessel [0041] The large mixing vessel used to prepare the blend prior to milling should be carefully checked at the end of Step 2.2 to ensure that no significant residues remain in the vessel. If significant residues are left behind they are likely to contain settled active ingredient. If this has happened the vessel can be rinsed with some of the remaining water which is then pumped through the mill.

[0042] Heat [0043] If a high shear mixer is used for manufacture then it may cause the mixture to heat up. Care should be taken to avoid mixing for long periods.

[0044] Final Product [0045] A number of tests are undertaken on the final product candidate (Table 2). MT tests are taken from the CIPAC test schedule.

Table 2. Test to be undertaken on the final product

[0046] Physical and Chemical Properties of the Product [0047] The physical and chemical properties of the product candidate are provided (Table 3).

Table 3. Properties of product candidate of Table 1.7

[0048] Product Specifications [0049] Final product specifications of the product candidate are provided (Table 4). Table 4. Product specification

[0050] Content of active constituent - allowable variations [0051] The content of active ingredient in the product candidate and its allowable variance is reported Table 5.

Table 5. Content of active ingredient in product candidate and its allowable variance.

[0052] Batch analysis data [0053] A 5L batch of the product candidate was prepared in a pilot plant and compared with the proposed product specification (Table 6).

Table 6. Comparison of a 1L batch of the product candidate with proposed product specifications.

[0054] Stability data - Accelerated [0055] Stability testing - including cold temperature testing [0056] The product candidate described in table 1.7 was packed into HDPE bottles (500ml), sealed and placed at ambient, 54°C for 2 weeks and 0°C for 1 week. These samples were then assessed for physical stability (Table 7).

Table 7. Physical stability of table 1.7 material after storage at ambient, 1 week @ 0°C and 2 weeks @54°C.

[0057] Active Ingredient Stability [0058] The product candidate was packed into HDPE bottles and stored at; ambient, 54°C for 2 weeks and 0°C for 1 week. Active content was analysed by HPLC both prior to and at the completion of this accelerated storage stability test (Table).

The active ingredient was stable under these test conditions.

Table 8. Active ingredient stability product candidate (described in table 1.7) stored in HDPE bottles at ambient, 2 weeks at 54°C and 1week at 0°C.

[0059] Packaging stability [0060] The HDPE containers and their labels remained unchanged when stored at ambient, 0°C for 1 week and at 54°C for 2 weeks.

[0061] Flutriafole Field Trial Data [0062] Trial 1 [0063] A trial was established during winter 2013 (10/7/13) to determine the crop safety and bioefficacy of two formulations of flutriafol when applied as a fertiliser dressing (fungicide amended fertiliser).

[0064] Using 80 kg/ha Mon Ammonium Phosphate (MAP) as a base rate treatment lots were prepared by Eureka! AgResearch Pty Ltd using 2 formulations: • Whitestar Flutriafol 500 SC (Whitestar 500 SC) • Eureka Flutriafol 600 SC (Eureka 600 SC - see Table 1.7) [0065] The trial was established on H45 Wheat which is very prone to Stripe Rust (Puccinia striiformis). The trial site was sown on the property of AGF Seeds at Smeaton in central Victoria.

[0066] No adverse effects on crop growth in terms of plant counts, vigour ratings or phytotoxicity were noted in the time up to the first disease assessment.

[0067] On 29/10/13(111 day after sowing =DAS) the first Stripe rust infection was noted in wheat plots. At this stage barley was still relatively “clean” of disease with only a minor infection of Net blotch (Spot form).

[0068] A tiller assessment of Stripe Rust on 118 DAS indicated significant control by all applied treatments with very little difference between Whitestar 500 SC and Eureka 600 SC formulations. All rates of application provided significant control with very little difference between rates (see chart in Figure 1). A subsequent assessment on 18/11/13 (131 DAS) examining % leaf.

[0069] In Figure 1 the treatments referred to in the columns from left to right are as follows: 1. Untreated control 2. Whitestar 500 SC 300 3. Whitestar 500 SC 400 4. Whitestar 500 SC 480 5. Whitestar 500 SC600 6. 600 SC 250 7. 600 SC 333 8. 600 SC 400 9. 600 C 500 [0070] Area infected revealed similar large differences in disease control between untreated and all applied treatments.

[0071] Summary of Results (trial 1) • Flutriafol applied as a fertiliser amended treatment in both Whitestar 500 SC and Eureka 600 SC formulations provided significant in - crop control of Stripe Rust. • Both Whitestar 500 SC and Eureka 600 SC were equivalent in their performance vs Stripe rust. • Both formulations require at least 200 g a.i/ha to provide ultimate control of Stripe rust. • In-crop disease control was not translated into positive wheat yield responses.

[0072] ASSESSMENTS

[0073] PLANT COUNTS

Plants numbers from 2 x 1 m2 quadrats were taken and converted into Plants/m2 at 43 DAS for both crops.

[0074] DISEASE

[0075] Wheat. 1st assessment (118 DAS).

[0076] 10 whole plants were sampled directly from plots in a random pattern, bagged for later assessment. 2 main tillers from each plant were then taken and each tiller assessed for the presence of Stripe rust giving at least 20 tillers. Tillers were then classed as either infected/non infected and % calculated.

[0077] Wheat. 2nd assessment (131 DAS).

[0078] 10 whole plants were sampled directly from plots in a random pattern, bagged for later assessment as per assessment 1. 1 -> 2 main tillers from each plant were then taken and each tiller assessed for the presence of Stripe rust on Leaf 1 (uppermost leaf), Leaf 2 and Leaf 3. For each leaf a % leaf area infected rating was recorded using a comparative scale. Averages were then calculated for each plot.

Table 9 - Treatments

Table 10 - Stripe Rust incidence (% tillers infected) Wheat. 5/11/13 (118DAS)

[0079] The results are also presented in the column chart of Figure 2.

[0080] Comments [0081] Stripe rust was first observed on site on 29/10/13. All treatments showed some level of Stripe rust present which indicates the susceptibility of H45 to the disease.

[0082] Almost complete infection of untreated was observed with high levels of leaf infection (to be assessed at next assessment).

[0083] All applied treatments provided significant control of the Stripe rust. Both formulations appeared equivalent in efficacy and both produced a slightly discernible dose response.

[0084] There was a preference for treatments 3-5, 7-9 (i.e. at least 200 g a.i/ha). 150 g a.i/ha was probably inferior in providing slightly higher levels of disease compared to other treatments.

[0085] Trial 2 [0086] Two field trials were established at “Mylandra Park”, Grenfell, New South Wales to evaluate the efficacy and crop safety of Flutriafol when applied as a fertiliser dressing treatment for the control of Stripe Rust (Puccinia striiformis) in wheat and Scald in Barley (Rhychosporium secalis).

[0087] The treatments applied in the trials were as follows: 1. Untreated 2. Whitestar 500SC @300ml/ha 3. Whitestar 500SC @400ml/ha 4. Whitestar 500SC @480ml/ha 5. Whitestar 500SC @600ml/ha 6. Eureka 600 SC @250ml/ha 7. Eureka 600 SC @333ml/ha 8. Eureka 600 SC @400ml/ha 9. Eureka 600 SC @500ml/ha [0088] The following was concluded from the trials: • Plant emergence at 14DAS has displayed no statistical difference between treatments for wheat. Numerically, Whitestar 500SC @300ml/ha and 400ml/ha has displayed the highest plant counts. A statistical treatment difference for barley plant emergence has been noticed with both Whitestar 500SC @480ml/ha and Eureka 600 SC @250ml and 400ml/ha displaying the highest plant emergence counts and proving statistically superior to Whitestar 500SC @300ml/ha and the untreated control. • The addition of Flutriafol applied as a fertiliser dressing treatment has shown to produce statistical differentiation between treatments for Stripe Rust control in wheat at all assessment dates. At trial completion, numerically Eureka 600 SC @500ml/ha has displayed the lowest disease presence when compared to all treatments. At the same period for barley scald, all treatments have proven to be statistically similar and superior to that of the untreated control. Numerically, Whitestar 500SC @400ml/ha displayed the lowest disease at 130DAS. • There has been no statistical treatment difference for Flutriafol fertiliser treatments for both wheat and barley in regards to yield response. The greatest yield responses have been observed on barley with all Eureka 600SC treatments displaying a greater increase over the Whitestar 500SC all treatments, Eureka 600 SC @ 225ml/ha has displayed a 32.87% yield advantage over that of the untreated control. • There have been no adverse treatment effects in regards to crop emergence, crop development and plant phytotoxicity responses on both wheat and barley with the treatments and rates utilised within these trials.

Table 10 - Target Pest

Table 11 - Product Information

Table 12 - Treatments

Table 13 - Assessment Techniques [0089] Assessment Methods for Phytotoxicity and Efficacy

[0090] Results [0091 ] Wheat

Table 14 - Table of Means - Wheat plant emergence at 14DAS.

[0092] Index: • ns = no significant difference at a 95% Confidence Interval

Table 15 - Table of Means - Percentage plant infection of Stripe Rust (Puccinia striiformis) at 100, 120 & 130DAS.

[0093] Index: • Letters indicate level of significance. Treatments with differing letter designations indicate a difference in efficacy on the crop in question.

Table 16 - Table of Means - Wheat Yield (kg/ha).

[0094] Index: • ns = no significant difference at a 95% Confidence Interval [0095] Bariev

Table 17 - Table of Means - Barley plant emergence at 14DAS.

[0096] Index: • Letters indicate level of significance. Treatments with differing letter designations indicate a difference in efficacy on the crop in question.

Table 18 - Table of Means - Percentage Scald in Barley (Rhychosporium secalis) plant infection at 100,120 and 130DAS.

[0097] Index: • Letters indicate level of significance. Treatments with differing letter designations indicate a difference in efficacy on the crop in question. • ns = no significant difference at a 95% Confidence Interval

Table 19 - Table of Means - Barley Yield (kg/ha).

[0098] Index: • ns = no significant difference at a 95% Confidence Interval [0099] Conclusions • Plant emergence at 14DAS has displayed no statistical difference between treatments for wheat. Numerically, Whitestar 500SC @300ml/ha and 400ml/ha has displayed the highest plant counts. A statistical treatment difference for barley plant emergence has been noticed with both Whitestar 500SC @480ml/ha and Eureka 600 SC @250ml and 400ml/ha displaying the highest plant emergence counts and proving statistically superior to Whitestar 500SC @300ml/ha and the untreated control.

The addition of Flutriafol applied as a fertiliser dressing treatment has shown to produce statistical differentiation between treatments for Stripe Rust control in wheat at all assessment dates. At trial completion, numerically Eureka 600 SC @500ml/ha has displayed the lowest disease presence when compared to all treatments. At the same period for barley scald, all treatments have proven to be statistically similar and superior to that of the untreated control. Numerically, Whitestar 500SC @400ml/ha displayed the lowest disease at 130DAS.

There has been no statistical treatment difference for Flutriafol fertiliser treatments for both wheat and barley in regards to yield response. The greatest yield responses have been observed on barley with all Eureka 600 SC treatments displaying a greater increase over the Whitestar 500SC all treatments, Eureka 600 SC 225ml/ha has displayed a 32.87% yield advantage over that of the untreated control.

There have been no adverse treatment effects in regards to crop emergence, crop development and plant phytotoxicity responses on both wheat and barley with the treatments and rates utilised within these trials.

Claims (8)

1. Claims

   1. An aqueous flutriafol suspension concentrate composition comprising: (a) flutriafol in an amount of at least 550g/L of concentrate composition; (b) water in an amount of less than about 400 g/L of concentrate composition; and (c) a surface active agent composition comprising at least one selected from the from the group consisting of (i) comb-graft copolymers wherein the graft component comprises polyethylene oxide moieties and the backbone component comprises (in polymerised form) acylic or methacylic acids or salts or esters thereof (ii) linear copolymers of an oily monomer and an acrylic or methacylic or maleic acid monomer, or anionic salts thereof and (iii) alcohol ethoxylates.
2. 2. The aqueous flutriafol suspension concentrate composition according to claim 1 comprising at least one surfactant selected from the group consisting of: (i) the alcohol ethoxylate surfactant in an amount of froml 5-120 g/L of the concentrate composition wherein the alcohol ethoxylates are selected from Ci2 - C-i4 alcohol ethoxylates or blends thereof; (ii) the comb-graft surfactant in an amount of from 10-70 g/L g/L of the concentrate composition; and (iii) the polycarboxylate surfactant in an amount of from 3-25 g/L of the concentrate composition.
3. 3. The aqueous flutriafol suspension concentrate composition according to claim 1 or claim 2 comprising surface active agents selected from at least two of the groups (i), (ii) and (iii).
4. 4. The aqueous flutriafol suspension concentrate according to any one of claims 1 to 3 comprising surface active agents from each of the groups (i), (ii) and (iii).
5. 5. The aqueous flutriafol suspension concentrate of any one of claims 1 to 4 further comprising glycerol or propylene glycol in an amount of from 40-150 g/L of the concentrate composition.
6. 6. The aqueous flutriafol suspension concentrate of any one of claims 1 to 5 further comprising smectite in an amount of at least 1 -12 g/L of the concentrate composition.
7. 7. The aqueous flutriafol suspension concentrate of any one of claims 1 to 6, wherein the weight ratio of flutroafol active agent to water is greater than 1.4/1.
8. 8. A method of preventing or controlling fungal infestation in plants comprising applying to the site at which infestation is to be prevented or controlled a composition according to any one of the previous claims, optionally diluted with water prior to applying.