AU686552B3 - Herbicide, crop desiccant and defoliant adjuvant - Google Patents

Description

J41

P/00/009 Section 29(1) Regulation 3.1(2) AUSTRALIA

PatentsAct 1990

We Victorian Chemicals International Pty Ltd 37-49 Appleton Street, Richmond Vic 3121

and Wilbur-Ellis Company 2903 South Cedar Avenue, Fresno California, United States of America

being the applicants in respect of Australian petty patent application no. 36062/97 state the following:

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1. The persons nominated for the grant of the patent have entitlement fr-m the actual inveniors by virtue of the inventors employment by the applicants. a..

2. The persons nominated for the grant of the patent are the applicants of the basic 0 0e a application listed on the patent request form. 0

The basic application listed on the request form is the first application made in a Convention country in respect of the invention.

1-9 (Signature) (Date)

Position within the applicant Name of Signatory Position within the applicant

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(Signature) (Date)

Name of Signatory Position within the applicant

S111illIII l lil l1111111 111111111 11111ii 1 AU9736062

(12) PATENT ABRIDGMENT (11) Document No. AU-B-36062/97 (19) AUSTRALIAN PATENT OFFICE (10) Acceptance No. 686552 (Australian Petty Patent) (54) Title HERBICIDE, CROP DESICCANT AND DEFOLIANT ADJUVANT International Patent Classification(s) (51)6 A01N 025/02 A01 N 025/30 (21) Application No.: 36062/97 (22) Application Date: 28.08.97 (43) Publication Date 06.11.97 Publication Date of Granted Application 05.02.98 (62) Related to Division(s) 66400/94 (71) Applicant(s) VICTORIAN CHEMICAL INTERNATIONAL PTY LTD; WILBUR-ELLIS COMPANY (72) Inventor(s) ROBERT WILLIAM KILLICK; PETER RONALD WRIGLEY; PETER WILLIAM JONES; DAVID THOMAS SCHULTEIS (74) Attorney or Agent McMASTER ASSOCIATES 24 Park Street, SOUTH YARRA VIC 3141 (56) Prior Art Documents AU 40236/89 AU 53806/90 (57) Claim

1. An adjuvant composition for use with a herbicide, crop desiccant or defoliant including:

one or more ethyl esters of fatty acids having a level of unsaturation of at least and

(ii) one or more non-ionic emulsifiers and essentially no other type of emulsifier being present.

P/00/0 II Regulation 3.2

AUSTRALIA

PatentsAct 1990

ORIGINAL COMPLETE SPECIFICATION PETTY PATENT

Invention title: HERBICIDE, CROP DESICCANT AND DEFOLIANT ADJUVANTS

*0

The following statement is a full. description of this invention, including the best method of S 5* performing it known to us: 4* P

S S S S* S HERBICIDE, CROP DESICCANT AND DEFOLIANT ADJUVANTS

Field of the Invention

This invention relates to compositions that are used as adjuvants to facilitate the effectiveness of herbicides, crop desiccants and defoliants. More particularly such compositions have proved most effective against post-emergent weeds during the growing of corn and soyabean crops, the desiccation of potato and alfalfa foliage and the defoliation of cotton leaves.

Background to the invention

To maximise crop yields it has become essential to eliminate competing growths to allow to the specific crops to grow unhindered. To this end the chemical industry has developed a range of herbicides to combat almost every weed. Similarly to facilitate mechanical harvesting it has been found necessary to either desiccate the foliage of potatoes and alfalfa or defoliate the cotton leaves before the cotton is plucked.

The man on the land knows however that no herbicide gives a complete strike rate so a burgeoning sub-industry has developed by which the efficacy of herbicides can be improved. Many names have been used to describe such compounds including "surfactants", "spreaders", "crop oil concentrates" and "spray adjuvants". To overcome the problem in gene-al for the industry and in particular for i.ts own herbicides the BASF organisation patented systems in 1989 (USP 4,834,908 "Antagonism Defeating Crop Oil Concentrates" and Australian Patent 625194 "Adjuvants for use with Crop Protection Agents"). These systems are based on a concentrate comprising in essence 20-90% of a fatty acid ester, 4- of an anionic surfactant selected from the partial sulphate and phosphate esters of ethoxylates and from 7-20% of a fatty acid. A 100 parts of this blend is added to 140 parts of a hydrocarbon.

In the field, the system has been by-passed by the use of the simple methyl fatty esters emulsified with non ionic surfactants,

Another approach has been disclosed in an article entitled "Small Grass and Grass Weed Response to BAS-514 with Adjuvants" (Manthey et al) in Volume 4 Issue 2 of Weed Technology. The use of methyl, ethyl and butyl esterified sunflower oil is discussed as adjuvants for BASJ 14. This study showed enhancing of BAS-514 by their use. There was no noted significant difference in efficacy between methyl, ethyl and butyl esters. It is recognised that even these products are not optimising the efficacy of the herbicides. To facilitate the gathering of potatoes and alfalfa seed, current practice is to desiccate the growing plants' foliage before harvest. Certain cationic materials are recommended with products such as DES-I-CATE and DIQUAT HERBICIDE H/A being well known on the field. It has also been found that their effectiveness may be enhanced by use of adjuvants such as AD-IT which is based on emulsified methyl oleate.

Similar to the current adjuvants for herbicides neither the total effectiveness, nor the rate of the desiccation is completely satisfactory for the farmer.

While the mechanical harvesting of crops such as cotton, tomatoes and beans has lowered 15 production costs, it has also created new problems. In the case of cotton, mechanical harvesting has created perplexing problems at gins and textile mills. Such mechanically harvested cotton absorbs moisture from the spindles of the harvester and contains

considerably more than the normal 5 to 15 percent of trash present in hand-picked cotton. Particularly bothersome is leaf material which is one of the most difficult types of trash to remove. This additional moisture and trash in mechanically harvested cotton frequently *"*"complicates ginning operations and raises the costs of textile manufacturing by requiring additional steps in cleaning the cotton at the mill.

Recent efforts have been directed toward the development of various chemical treatments S.i for the crop plant in an effort to overcome the objectionable attributes of mechanically harvested cotton. For example, processes have been suggested in recent years which have as their objective to provide increased yields of the desired crop and/or to inhibit rank growth. Such processes have been effective in some respects. However, some of the prior art methods require the use of expensive surfactants in order to obtain satisfactory application of the chemical piroduct to the plant. Other prior art methods produce an insufficient increase in the crop yield and/or decreases in rank growth for economic utilisation.

As the answer to this need, a plant growth regulator and its method of use were patented in 1984 "Plant Growth Regulator and Method for the Use Thereof" (USP 4,439,224), Whilst significant improvement was achieved, decreased trash limits continue to be set by the mills demanding further improvements in the level of defoliation.

Summary of the Invention

It has now been surprisingly found that certain blends enhance the activity of herbicides, crop desiccants and defoliants. Accordingly, an adjuvant composition is provided for use with a herbicide, crop desiccant or defoliant including: one or more ethyl esters of fatty acids having a level of unsaturation of at least and (ii) one or more non-ionic emulsifiers and essentially no other type of emulsifier being present. Preferably, no other type of emulsifier is present.

15 The higher levels of unsaturated fatty acids are preferred, being more effective as penetrants. Preferably the ethyl esters comprise at least 50% by weight of the composition. Other alkyl esters may be present in addition to ethyl esters.

There are innumerable variations of the preferred ethyl ester since the ethyl esters of fatty acids may be produced from the natural oils and fats such as lard, tallow and vegetable oils or from specific blends produced by fatty acid manufacturers or from fatty acids produced by synthetic means. Readily available commercial vegetable oils such as canola, corn, sunflower and soyabean oils are also sources for fatty acids. Such fatty acids will generally 9be described in this patent specification as unsaturated fatty acids or oleates.

The non-ionic emulsifiers are well known to those skilled in the art, and it is recognised there are a multitude of combinations. Preferably a non-ionic ester of the fatty acid moiety provides unexpected emulsification and coupling effects to furnish a finished homogeneous

product,

The ethyl esters and non-ionic emulsifier work in synergy firstly to provide the right emulsification characteristics of the alkyl esters present in the composition and secondly to modify the surface properties of the plant foliage to maximise the ingress of the active ingredient, i.e. the herbicide, desiccant or defoliant. The emulsifier may be a combination of two or more non-ionic emulsifiers.

In another preferred embodiment, the non-ionic emulsifiers are a combination of alkylaryl ethoxylate and a polyethyleneglycol (PEG) ester of fatty acids. Preferably, the alkylaryl ethoxylate is octyl, nonyl or dodecylphenol with 3 to 13 moles of ethylene oxide, whilst the PEG ester is of molecular weight range 200-600 with either one or two moles of unsaturated fatty acids. Whilst it is acknowledged that the emulsifiers outlined above cover a wide range of physical properties and provide wide ranging emulsification abilities, it is important to note that a balance between two quite different emulsifiers can produce a far greater effect than an intermediate emulsifier. With this in mind, many combinations of alkylaryl ethoxylates and PEG esters can provide adequate emulsification of alkyl esters of unsaturated fatty acids for adjuvant systems. A preferred combination is ethoxylated nonylphenol with 9 moles of ethylene oxide and PEG 400 di-ester in the ratio 1:2 by weight. In another preferred embodiment, the non-ionic emulsifier is the ethoxylated soya-amine base. A preferred emulsifier would have 15 mole ethoxylation. In other preferred embodiments, other non-ionic emulsifiers of interest are those based on the fatty alcohols. A preferred emulsifier would have 6 mole ethoxylation on the 12 carbon alcohol. The present invention also extends to mixtures of the adjuvant composition with herbicides, crop desiccants, defoliants, or agricultural chemicals.

The adjuvant compositions are used to penetrate or soften the waxy protective layer of the plant's foliage. Several methods have been developed to determine an ingredient's penetrative, "softening" or solvent power. The most appropriate laboratory technique evolved by the petroleum oil industry is a method, called the Aniline Point, which is specifically used to determine the solvent power of cleaners, thinners, etc. From multitudinous studies, it is well known that as the molecular weight of a paraffin oil increases, the Aniline Point increases and the solvent power decreases. By way of example. set out below is information taken from "Exxon Chemical Performance Products for Pesticides".

Paraffin Molecular Aniline Content Weight Point (Avge) (oC)

Norpar (RTM) 12 99.1 163 82 Norpar (RTM) 13 99.4 189 87 Norpar (RTM) 15 99.1 212 92

Similar results are seen with the alkyl esters of the unsaturated fatty acids, in this case the oleates from canola oil. Because of these products' solvent power the test undertaken is the Mixed Aniline Point.

Molecular Mixed *c Weight Aniline (Avge) Point 0 C)

Methyl Oleate 296 -8.4 Ethyl Oleate 310 0.0 iso-Propyl Oleate 324 +5.4 *1 n-Butyl Oleate 338 +10.0 S. 5@ 0 Based on these results, it would be expected that the most effective oil blend would be based on methyl oleate. Against this technical expectation, it has been surprisingly found that the preferred oil blend is based on the ethyl oleate mixture as seen in the Examples in combination with non-ionic emulsifiers.

Examples

The effectiveness of the compositions of the invention have been subject to a series of trials.

Product blends were made as follows:

Composition 1 HASTEN w/w) Ethyl Oleate (80%w/w ethyl oleate and 20%w/w 76 methyl oleate) PEG 400 di-oleate 16 Nonyl phenol ethoxylate (9EO) 8 Composition 2

VICC EM EOD w/w) a

Ethyl Oleate (80%w/w ethyl oleate and 20%w/w aa methyl oleate) Soya-amine ethoxylate (15 EO) an.r Composition 3 a VICCHEM a EOA ma a.

Ethyl Oleate (80%w/w ethyl oleate and 20%w/w methyl oleate) Fatty alcohol ethyoxylate (12A6) PEG 400 mono oleate

Herbicides The results shown in the Tables are the mean results from experiments conducted. The compositions were assessed against various weeds velvet leaf, common lambs quarters, giant foxtail, pig weed, spring amath, ivy leaf, morning glory and prickly sida. Velvet leaf is of most concern to the farmer being the most difficult to control.

After the non-treated control, the proprietary adjuvants tested included X-77 (a simple surfactant of a non-ionic blend of a nonyl ethoxylate and oleic acid); CAYUSE the original water based product of a blend of ammonium sulphate and phosphate ester; CAYUSE PLUS designed to meet the herbicide manufacturer's nitrogen recommendation a blend of ammonium sulphate, ammonium nitrate and phosphate ester; SUN-IT II methylated seed oil (methyl oleate) with nonionic emulsifiers; and HASTEN as is shown in Composition 1. TABLE 1 Herbicide: Pursuit (25 gram/acre (62g/ha)) Visual Injury .0 14 Days After Treatment Velvet Common Giant leaf Lamb Foxtail Quarters Non Treated Control 0 0 0 *9 X-77 41 45 46 9 CAYUSE (1 pint/acre (1.17 1/ha)) 67 44 68

*9*9 C CAYUSE PLUS (2 pints/acre (2.34 1/ha)) 70 38 78 SUN-IT II 28% N (2 pints/acre (2.34 1/ha)) 73 45 81 HASTEN 28% N (2 pints/acre (2.34 Vha)) 84 49 83 S 0

TABLE 2 I, *C*

Herbicide: Pursuit (25 gram/acre (62 g/ha)) Visual Injury 14 Days After Treatment Velvet Common Giant CO C leaf Lamb Foxtail 0 Quarters Non Treated Control 0 0 0 CAYUSE PLUS (2 pints/acre (2.34 1/ha)) 73 56 69 SUN-IT I (1.5 pints/acre (1.75 l/ha)) +28% N 71 49 89 (2 pints/acre (2.34 1/ha)) HASTEN (1.5 pints/acre (1.75 1/ha)) 28% N 83 68 100 (2 pints/acre (2.34 1/ha))

TABLE 3 Herbicide: Pursuit (25 gram/acre (62 g/ha)) Visual Injury 14 Days After Treatment Velvet Common Giant leaf Lamb Foxtail Quarters

Non Treated Control 0 0 0 X-77 41 56 61 CAYUSE (1 pint/acre (1.17 1/ha)) 74 61 81 CAYUSE PLUS (2 pints/acre (2.34 1/ha)) 70 43 74 SUN-IT II (2 pints/acre (2.34 1/ha)) 28% N 81 71 (2 pints/acre (2.34 1/ha)) *6 6 HASTEN (2 pint/acre (2.34 1/ha) 28 N 84 69 (2 pints/acre (2.34 1/ha))

o *0 TABLE 4

S Herbicide: Pursuit (4 ozs/acre (280 g/ha))

6 *S All Visual Injury

Days After Treatment

*5 Velvet Pigweed Spring leaf Amath S S. SO s Non Treated Control 0 0 0

CAYUSE (1 pint/acre (1.17 I/ha)) 36.3 81.3 96.5

CAYUSE PLUS (2 pints/acre (2.34 1/ha)) 31.3 77.5 96.5

HASTEN (2 pints/acre (2.34 1/ha)) 28% N 51.3 85.8 99.5 (2 pints/acre (2.34 1/ha))

TABLE

Herbicide: Classic/Pinnacle (0.25 oz/0.25 ozlaere (17.5 g/ha))

All Visual Injury

Days After Treatment

Velvet Pigweed Prickly leaf Sida

Non Treated Control 0 0 0

CAYUSE (0.5 pints/acre (585 ml/ha)) 37.5 90.0

CAYUSE PLUS (1 pint/acre 171l/ha)) 52.5 86.3 11.3

HASTEN (1/6 pints/acre;195 mi/ha)) 28% 50 83,8 12,5

C C C (1 pint/acre 17 i/ha)) ec

Ge C

C.

SC C TABLE 6 CC CC C C C Herbicide: Beacon (0.76 oz/acre (53 glha. on corn crops))

C All Visual Injury *0~ C C

26 Days After Treatment

Velvet Ivy leaf/' Giant C leaf Morning Foxtail Glory C C. C SUPERB (methylated seed oil) 88 65 GC C CC (1 qt/acre (2.34 i/ha))

HASTEN (1 qt/acre (2.34 i/ha)) 93 85

11.

TABLE 7

Herbicide: Pursuit (4 oz/acre (280 g/ha on soybean crops))

All Visual Injury

26 Days After Treatment

TABLE 8 4

*O 4 Herbicide: Accent (0.023 pound active ingredient/acre (25.7g/ha)) 0 0 *0*0

4000 0000 All Visual Injury 04 21 Days After Treatment

.4 000

*s 0 000*

10 ECHCG Barn yard grass 0

SETLU Yellow foxtail

SETVI Green foxtail

SETFA Giant foxtail

The test results in Tables 1 to 8 (inclusive) show that the HASTEN composition compared to other adjuvants caused greater visual injury with a larger variety of weeds tested and in conjunction with a large variety of commercially available herbicides.

Desiccants

To facilitate the gathering of potatoes and alfalfa seed for example, current practice is to desiccate the growing plants' foliage before harvest. Certain cationic materials are recommended with products such as DES-I-CATE and DIQUAT HERBICIDE H/A being well known on the field.

Potato foliage was sprayed 10 to 14 days prior to harvest with, for ground application, about 600 ml per acre for DIQUAT HERBICIDE and around 9.6 litres per acre (23.7 1/ha) for DES-I-CATE in 96 to 480 litres of total spray.

To improve the efficacy of these desiccants AD-IT [a proprietary product from the Wilbur Ellis Company] was added to the solution to provide 9.6 litres of AD-IT adjuvant per acre (23.7 1/ha). AD-IT is a blend of methyl oleate and a mixture of nonionic emulsifiers,

A trial was conducted comparing this material against a composition known as VICCHEM EOD (see Composition 2) at the same usage rates noted above Visual rating was undertaken at 10 and 14 days, See Table 9.

15 TABLE 9

Visual Injury

:0*0 10 days 14 days

AD-IT average average

0 VICCHEM EOD superior above average

S. Defoliants

The traditional and still widely used method of defoliation of cotton uses sodium chlorate with or without the cationic PARAQUAT, In newer techniques specific defoliants such as DROPP, (thidiazuron, a substituted urea) and the organo phosphate FOLEX are used. At the time these defoliants are sprayed onto the cotton bushes several ingredients are incorporated in the spray solution. These include PREP (a boll opener), BIVERT(RTM), a drift control and depostition retention agent), MOR-ACT (a crop oil concentrate based on petroleum oil and surfactants), SYLGARD(RTM) 309 (an organo silicon surfactant),

13.

TRISERT CB (an organo nitrogen product providing 26% Nitrogen) and R-11 (a proprietary nonionic surfactant). HASTEN is that shown in Composition 1.

Defoliation figures show the leaves that have fallen from the plant. Desiccation shows the level of leaves still on the plant but expected to fall soon. The open bolls show the cotton pods which are open and ready to be picked.

The first set of trials were undertaken in Shafter County, California. All treatments were applied at 20 gallons/acre (187 1/ha) by ground spray and results were assessed after 9 days, See Table

TABLE

Treatment #1 #2 #3 #4 #5 #6

DROPP (lbs/acre 0.2/ 0.2/ 0.2/ 0.2/ 0.2/ 0.2/ 224 224 224 224 224 224

o PREP (qt/acre 1/2.34 1/2.34 1/2.34 1/2.34 1/2.34 1/2,34

00 BIVERT (pt/acre (ml/ha)) 0.75/ 0.75/ 0.75/ 0.75/ 0.75/ 0.75/ 877 877 877 877 877 877 0

000 MOR-ACT (pt/acre 1/1.17 1/1.17 0e

SYLGARD (pts/l100gal (1/800 2 4 2 4

TRISERT (gal/100al. (1/100 1 0

0* HASTEN (pints/100gal (1/800 4 8 0* 0

00 0 Defoliation 58.9 50.9 68.9 71.4 80.9 83.6 0 *r 0

Desiccation 0.7 1.0 1.0 7.5 2.6 10,0

Open bolls 84.0 86.8 91.5 89.0 94.9 94.6

A second set of trials were undertaken in Fresno County, California. All trials were applied at 30 gallons/acre (281 I/ha) by ground spray and results were assessed after 11 days. This was an extreme trial as the cotton plants had excess vegetation from over-fertilisation and watering. See Table 11.

TABLE 11

Treatment #1 #2 #3 #4

FOLEX (pint/acre 3/3.51 3/3.51 3/3.51 3/3.51 3/3.51

PREP (pint/acre 2/2.34 2/2.34 2/2.34 2/2.34 2/2.34

BIVERT (pint/acre 1/1.17 1/1.17 1/1.17 1/1. 17 1/1.17,

MOR-ACT (pint/acre 1/1.17 1/1.17 1/1.17

SYLGARD (pint/acre 4/4.68 4/4.68

TRISERT (gal/lO0gal (11100 1 4

HASTEN (pints/1O0gal (1/800 8 4

Defoliation 37.9 49A4 55.4 51.4 4731

Desiccation 14.5 30.7 45,9 47.2 29.5

Vo Open boils 47.7 57.8 70.0 54.8 64.8

a

The third set of trials were again undertaken in Fresno County, California. All trials were *0 applied at 20 gallons/acre (187 1/ha) by ground spray and results were assessed after 7 days. .0.

See Table 12.

TABLE 12

Treatment #1 #2 #3 #4

FOLEX (pint/acre 2/2.34 2/2.34 2/2.34 2/2.34 2/2.34

PREP (pint/acre 2/2.34 2/2.34 2/2.34 2/2.34 2/2.34

BIVERT (pint/acre (ml/ha)) 0.5/585 0.5/585 0.5/585 0.5/585 0.5/585

R-11 (pint/100gal (1/800 2

SYLGARD (pint/100gal (1/800 2 2 4 4

HASTEN (pint/100gal (1/800 4 8

Defoliation 87.5 77.6 87.3 83.4 89,1

Desiccation 23.3 6.5 9.8 13.2 21.2

Open bolls 77.4 70.4 69.6 76.5 68.3

A major field trial was conducted at the K5 cotton field at "The Gardens" Wee Waa Australia. The field was divided into two 33 hectare blocks East and West. The western side was treated with the following formulation.

D C Tron Oil 2 litres/ha

DROPP 100gm/ha

Dimethoate 500ml/ha

D C Tron Oil is an emulsified paraffinic petroleum oil and is used throughout the district. The product was applied by aerial spray at a water volume of 20 litre/hectare. The to temperature was 20°C, humidity 75% and wind at a 5 knot northerly.

For the eastern side HASTEN (see Composition 1) was directly substituted for D C Tron Oil at the same volume. Significant leaf defoliation differences were observed as follows where senesced leaf is classified as a leaf which falls from the plant when flicked with the finger. See Table 13.

r-rr~--nr~ rr~- rr~nars~- n~-aa~l

TABLE 13

East-HASTEN West-D C Tron

Green Leaf Senesced Leaf Green Leaf Senesced Leaf 1I .1 I Pre-Spray 4- 1 days 4 19 26

9 days 2 5 12 4 t 1 r

12 days 0 3 1 6

Percentage of Green Leaves Remaining

*9 9 East-HASTEN West-D C Tron a,

Green Leaf Senesced Leaf Green Leaf Senesced Leaf 9 9

days 3% 16% *C 9

9 days 1% 7%

12 days 0% 4%

99 4

99.. It was observed that green leaf drop was faster and more complete in the eastern side (ie. treated with HASTEN). This was particularly obvious in the 5 day assessment. S9 9 *4

9* Consequently as the defoliation was relatively quick, picking can commence earlier and also achieve better grades of cotton through the absence of foliage.

17. Thie claims defining the invention are as follows:

1. An adjuvant composition for use with a herbicide, crop desiccant or defoliant including;

one or more ethyl esters of fatty acids having a level of unsaturation of at least and

(ii) one or more non-ionic emulsifiers and essentially no other type of emulsifier being present.

2. A composition according to claim I wherein no other type of emulsifier is present,

3. A composition according to claim I wherein the non-ionic emulsifiers is a polyethyleneglycol (PEG) ester of fatty acids and/or of the akylarylethoxylate type.

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18.

ABSTRACT

An adjuvant composition for use with a herbicide, crop desiccant or defoliant including:

one or more ethyl esters of fatty acids having a level of unsaturation of at least and

(ii) one or more non-ionic emulsifiers and essentially no other type of emulsifier being present.

see a

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