WO 2007/050090 Al

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual Property OrganizationInternational Bureau

(43) International Publication Date (10) International Publication Number3 May 2007 (03.05.2007) PCT WO 2007/050090 Al

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for everyAOlN 25/30 (2006.01) AOlN 43/14 (2006.01) kind of national protection available): AE, AG, AL, AM,AOlN 35/10 (2006.01) AOlP 13/00 (2006.01) AT,AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,AOlN 37/36 (2006.01) CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI,

GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE,(21) International Application Number:KG, KM, KN, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV,PCT/US2005/039443LY,MA, MD, MG, MK, MN, MW, MX, MZ, NA, NG, NI,

(22) International Filing Date: 28 October 2005 (28.10.2005) NO, NZ, OM, PG, PH, PL, PT, RO, RU, SC, SD, SE, SG,

(25) Filing Language: English SK, SL, SM, SY, TJ, TM, TN, TR, TT, TZ, UA, UG, US,UZ, VC, VN, YU, ZA, ZM, ZW

(26) Publication Language: English

(71) Applicant (for all designated States except US): VALENT (84) Designated States (unless otherwise indicated, for every

U.S.A. CORPORATION [US/US]; 1600 Riviera Ave., kind of regional protection available): ARIPO (BW, GH,

Suite 200, P.O. Box 8025, Walnut Creek, California 94596 GM, KE, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM,

(US). ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),European (AT,BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,

(72) Inventors; and FR, GB, GR, HU, IE, IS, IT, LT, LU, LV,MC, NL, PL, PT,(75) Inventors/Applicants (for US only): KARCZEWSKI, RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA,

Alkesander, E. [US/US]; 2124 McKinley Avenue, No. 18, GN, GQ, GW, ML, MR, NE, SN, TD, TG).Berkeley, CA 94703 (US). LIU, Jane, Qing [US/US]; 356Montecito Way, Milpitas, California 95035 (US). TAY¬ Published:LOR, Evelyn, Jean [US/US] ; 203 Majorca Drive, San R a — with international search reportmon, California 94582 (US).

(74) Agents: BOLAND, Mark et al; SUGHRUE MION, For two-letter codes and other abbreviations, refer to the "G uid

PLLC, 2100 Pennsylvania Ave., N.W , Suite 800, Wash ance Notes on Codes and Abbreviations" appearing at the beg inington, DC 20037-3213 (US). ning of each regular issue of the PCT Gazette.

(54) Title: HERBICIDAL COMPOSITIONS

(57) Abstract: The present invention provides an improved herbicidal composition that substantially excludes anionic surfactantsselected from the dialkylmetalsulfosuccinate and the metal alkylaromatic sulfonates. The improved herbicidal composition includes(a) an effective amount of an herbicidal cyclohexanedione oxime compound or agriculturally acceptable salt or ester thereof, (b) oneor more esters of a fatty acid, (c) one or more nonionic surfactants, and optionally one or both of (d) an anionic surfactant other thana dialkylmetalsulfosuccinate or a metal alkylaromatic sulfonate, and (e) a hydrocarbon solvent. The present invention also providesmethods for controlling the growth of vegetation, by applying to the vegetation the composition of the present invention.

HERBICIDAL COMPOSITIONS

FIELD OF THE INVENTION

[01] The present invention relates to herbicidal compositions. More particularly, the

present invention relates to improved adjuvant-containing formulations suitable as

postemergent herbicides which improve the efficacy of herbicides.

BACKGROUND OF THE INVENTION

[02] It is known that herbicidal compositions containing cyclohexanedione oxime

compounds such as clethodim, sethoxydim, alloxydim, cycloxydim, butroxydim,

tralkoxydim, tepraloxydim, and profoxydim are difficult to formulate, since the active

ingredients are sensitive to chemical instability. Many adjuvant materials, surfactants, and

even water, for example, can lead to significant chemical degradation. Because chemical

stability is commercially desirable, as well as required by the Environmental Protection

Agency, it is common in the agricultural chemical industry to formulate cyclohexanedione

oxime compounds with an emphasis on chemical stability and good mixing characteristics,

rather than on optimization of herbicidal efficacy.

[03] Current graminicides typically require the addition of oil-based adjuvants (known as

"crop oil concentrates") in order to achieve commercially acceptable stability and weed

control. In particular, herbicidal efficacy for cyclohexanedione oxime compounds requires

adding crop oil concentrates at the time of application in the grower fields. Rather than

having to prepare a tank mix from separate herbicide and crop oil containers, it would be

commercially desirable to prepare herbicides and crop oils in one formulation which is ready

to dilute. However, because crop oil concentrates commonly used in the marketplace are

recommended at the use rate of 16 to 32 fluid ounces per acre, it has not been practical to

provide cyclohexanedione oxime compounds and crop oil concentrates as premixed, ready to

dilute formulations.

[04] Ready to dilute adjuvant-containing post-emergent herbicidal formulations are

described in U.S. Pat. No. 5,084,087. The formulation comprises a mixture of one or more

herbicidal compounds, a polyoxyalkylene nonionic surfactant having a hydrophilic-lipophilic

balance (HLB) of from 10 to about 14, an anionic surfactant selected from the dialkyl metal

sulfosuccinates and the metal alkylbenzene sulfonates, optionally a low foaming

polyoxyalkylene nonionic surfactant having an HLB of less than 10, and a lower alkanol ester

of a long chain fatty acid. This patent does not describe or suggest the particular herbicidal

compositions of the present invention or the advantageous properties described herein.

SUMMARY OF THE INVENTION

[05] An object of the present invention is to provide improved herbicidal compositions and

methods of use which exhibit excellent herbicidal efficacy and chemical stability.

[06] These and other objects and advantages of the present invention have been achieved

by providing an herbicidal composition comprising (a) an effective amount of an herbicidal

cyclohexanedione oxime compound or agriculturally acceptable salt or ester thereof; (b) one

or more esters of a fatty acid; and (c) one or more nonionic surfactant; wherein said

composition substantially excludes anionic surfactants selected from the

dialkylmetalsulfosuccinates and the metal alkylaromatic sulfonates. As additional, optional,

components, one or both of (d) an anionic surfactant other than a dialkylmetalsulfosuccinate

or a metal alkylaromatic sulfonate and (e) a hydrocarbon solvent can be used.

[07] In a preferred embodiment, the present invention provides an herbicidal composition

comprising (a) 10 to 30% by weight of clethodim; (b) 30 to 80% by weight of a mixture of

the methyl esters of C16-Cl 8 fatty acids; (c) 7 to 12% by weight of the nonionic surfactant;

and optionally (d) 5 to 50% by weight of an aromatic hydrocarbon solvent.

[08] In an additional preferred embodiment, the present invention provides an herbicidal

composition comprising (a) 10 to 30% by weight of clethodim; (b) 30 to 80% by weight of a

mixture of the methyl esters of C16-C18 fatty acids; (c) 1 to 5% by weight of the nonionic

surfactant; (d) 1 to 3% by weight of POE (5) tallow amine ether sulfate; and optionally (e) 5

to 50% by weight of an aromatic hydrocarbon solvent.

[09] In a further embodiment, the present invention provides methods for controlling the

growth of vegetation, comprising applying to the vegetation an effective amount of the

herbicidal composition described above.

DETAILED DESCRIPTION OF THE INVENTION

[10] The herbicidal compositions of the present invention offer several advantages,

including, for example, one or more of the following: they are chemically stable

formulations, they do not require the addition of a crop oil concentrate, they provide superior

control of susceptible weed species, provide increased speed of herbicide absorption and

herbicide symptoms, they result in increased speed of glyphosate absorption, and they can be

tank mixed with other herbicides without a decrease in weed control.

Cyclohexanedione Oximes

[11] The herbicidal ingredient of the present invention is an herbicidal compound having a

cyclohexanedione oxime structure. Certain cyclohexanedione oximes are known in the art as

having excellent herbicidal activity against a variety of post-emergent grasses in a variety of

environments. Typical examples include clethodim, sethoxydim, alloxydim, cycloxydim,

butroxydim, tralkoxydim, tepraloxydim, and profoxydim. Cyclohexanedione oximes can be

obtained on the market. For example, clethodim is provided by Valent U.S.A. Corporation or

Arysta LifeScience North America, sethoxydim and alloxydim are provided by Nippon Soda

Company or BASF Corporation, cycloxydim and profoxydim are provided by BASF

Corporation, and butroxydim is provided by CropCare Australasia. Alloxydim is usually

provided as its sodium salt. Preferred cyclohexanedione oximes are clethodim and

sethoxydim. Most preferred is clethodim. The active ingredient can be employed in several

technical forms such as Clethodim Technical (Valent U.S.A. Corporation or Arysta

LifeScience North America), which comprises 95.3% clethodim by weight and 4.7% inert

ingredients by weight, and a 70% or 37% by weight Manufacturing Use Product which is a

solution of Clethodim Technical in aromatic solvent. For any of the cyclohexanedione oxime

compounds which have an optically active center, such as clethodim, both racemic and

enantiomeric forms may be used as desired.

[12] The content of the herbicidal cyclohexanedione oxime compound in the herbicidal

compositions is preferably about 1 to 40% by weight, more preferably 3 to 30% by weight,

and most preferably 10 to 30% by weight.

Esters of a Fatty Acid

[13] The esters of a fatty acid are preferably C1-C8 alkyl (e.g. methyl, ethyl, isopropyl,

butyl, isobutyl, octyl) esters of a fatty acid. The fatty acids can be saturated or unsaturated

organic monobasic acids such as palmitic acid, myristic acid, stearic acid, lauric acid or oleic

acid. The carbon numbers of the fatty acids are preferably 12 to 22. Typical non-limiting

examples include methyl oleate, methyl palmitate, isopropyl myristate, octyl laurate,

isopropyl palmitate, and butyl stearate. The preferred esters of a fatty acid are a mixture

comprised predominantly of the methyl esters of C16-Cl 8 fatty acids.

[14] The C16-C18 fatty acid methyl ester mixture used in the herbicidal formulations

tested in the Examples set forth herein was CE-1618 (C16 23-32%, C18 65-75%, primarily

methyl oleate), available from Proctor and Gamble or AGNIQUE® ME 181-U (typically Cl 6

10%, Cl 8 84%, primarily methyl oleate), available from Cognis Corporation. Other suitable

esters of fatty acids include but are not limited to CE- 1695, CE- 1897, SE- 1885, also available

from Proctor and Gamble; other AGNIQUE® ME and AE products, available from Cognis

Corporation; STEPAN C-65 and C-68 and KESSCO® IPP, IPM and BS, available from

Stepan Company; and PRIOLUBE® 1530 and 1400, available from Uniqema.

[15] The content of the esters of a fatty acid in the herbicidal compositions of the present

invention is preferably about 10 to 90% by weight, more preferably 10 to 80% by weight,

even more preferably 20 to 80% by weight, and most preferably 30 to 80% by weight.

[16] The ratio of the esters of a fatty acid to the herbicidal ingredient is preferably 0.5 :1 to

25:1, more preferably 0.8:1 to 12:1, and most preferably 1:1 to 6:1.

Nonionic Surfactant

[17] Suitable nonionic surfactants include but are not limited to polyoxyethylene (POE)

derivatives of tallow or plant oils, POE sorbitan esters, ethylene oxide-propylene oxide (EO-

PO) block polymers, POE alkylphenols, polyoxyalkylene polyarylethers, ethoxylated

alcohols, POE fatty acid esters, alkyl polyglycosides and alkylpolysaccharides, POE fatty

amines, and polymeric surfactants. The HLB of the nonionic surfactant is preferably about

5.0 to 18.0.

[18] The POE derivatives of tallow or plant oils may be hydrogenated. Examples of the

plant oils include but are not limited to castor oil, rapeseed oil and linseed oil. A preferred

plant oil is castor oil. The POE castor oil surfactants used in the herbicidal formulations

tested in the Examples set forth herein were AGNIQUE® CSO-40 (POE (40) castor oil, HLB

13), AGNIQUE® CSO-30 (POE (30) castor oil, HLB 11.8), and AGNIQUE® CSO-1 6 (POE

(16) castor oil, HLB 8.6), available from Cognis Corporation. Other suitable POE derivatives

of tallow or plant oils include but are not limited to AGNIQUE® SBO, RSO and other CSO

products also available from Cognis Corporation; NINEX® MT-603, MT-610 and MT-615

and TOXIMUL® 8240, 8241, 8243, and 8244, available from Stepan Company;

EMULPON® CO 200, 904, and CO-360, available from Akzo Nobel; EMULSOGEN® EL

360, EL 400, EL-719, and HCO 040, available from Clariant Corporation; and

ALKAMULS® EL-620, OR-40, and EL-719, available from Rhodia.

[19] The POE sorbitan esters are preferably the ethoxylated sorbitan esters of fatty acids.

The fatty acid may be derived from animal or vegetable sources. Typical examples include

but are not limited to POE sorbitan monotallate, POE sorbitan monooleate, POE sorbitan

trioleate, POE sorbitan monostearate, POE sorbitan tristearate, POE sorbitan monomyristate,

and POE sorbitan monolaurate. A preferred POE sorbitan ester is POE (20) sorbitan

monooleate. The POE (20) sorbitan monooleate used in the herbicidal formulations tested in

the Examples set forth herein was AGNIQUE® SMO 20-U (HLB 15) available from Cognis

Corporation. Other suitable POE sorbitan esters include but are not limited to AGNIQUE®

SML, SMS, STS, and other SMO products, also available from Cognis Corporation;

ARMOTAN® SMO 20, available from Akzo Nobel; TOXIMUL® SEE-340 and 341,

available from Stepan Company; and ALTOX® 80 and 8916TF, TWEEN® 20, 40, 60, 65,

80, 81, and 85 available from Uniqema.

[20] Typical examples of EO-PO block polymers include but are not limited to block

copolymers of ethylene oxide and propylene oxide, EO-PO alkylphenol block polymers, EO-

PO butanol block polymers (polyoxyethylene-polyoxypropylene monobutyl ether), and EO-

PO ethylenediamine block polymers. The EO-PO block polymer used in the herbicidal

formulations tested in the Examples set forth herein was PLURONIC® L92 (block

copolymer of ethylene oxide and propylene oxide, average molecular weight 3650, HLB 6).

Other suitable examples of EO-PO block polymers are other surfactants from the

PLURONIC® L and P series, available from BASF Corporation; TOXIMUL® 8320 and

8323, available from Stepan Company; ATLAS® G-5000 and SYNPERONIC® PE series,

available from Uniqema; AGNIQUE® BP 4-3103, and BP NP-1530, available from Cognis

Corporation; ETHYLAN® NS 500 K and NS 500 LQ, available from Akzo Nobel;

TERGITOL™ XD, XH, XJ, available from The Dow Chemical Company; and

ANTAROX™ 724/P, SC/167, F-108, and P-104, available from Rhodia.

[21] Typical examples of POE alkylphenols include but are not limited to POE

nonylphenol, POE octylphenol, POE tributylphenol, POE dinonylphenol, and POE

dodcylphenol. The POE alkylphenols used in the herbicidal formulations tested in the

Examples set forth herein were MAKON® 4 (POE (4) nonylphenol, HLB 9) and MAKON®

8 (POE (8) nonylphenol, HLB 12), available from Stepan Company. Other suitable examples

of POE alkylphenols are MAKON® 10, 12, 14 and 30, and MAKON® OP-9, also available

from Stepan Company; SYNPERONIC® NP series, available from Uniqema; ARKOPAL®

N series, EMULSOGEN® 10, and SAPOGENAT® T 040, T060, T 080, and T IlO,

available from Clariant Corporation; AGNIQUE® NP and OP series, available from Cognis

Corporation; WITCONOL® NP series, available from Akzo Nobel; and IGEPAL™ CO,

CA, DM and RC series, available from Rhodia.

[22] Typical examples of polyoxyalkylene polyarylethers include but are not limited to

polyoxyethylene (POE) polyoxypropylene (POP) tristyrylphenols, and POE tristyrylphenols.

The polyoxyalkylene polyarylether used in the herbicidal formulations tested in the Examples

set forth herein was SOPROPHOR® 796/P (POE (21)/P0P (4) tristyrylphenol, HLB 13.5),

available from Rhodia. Other suitable examples of polyoxyalkylene polyarylethers are

EMULSOGEN® TS 160, available from Clariant Corporation; AGNIQUE® TSP 16,

available from Cognis Corporation; and SOPROPHOR® BSU and CY/8, available from

Rhodia.

[23] Typical examples of ethoxylated alcohols include but are not limited to POE C6-12

alcohol, POE C9-12 alcohol, POE C12-15 alcohol, POE C16-18 alcohol, POE lauryl alcohol,

POE oleyl alcohol, POE stearyl alcohol, POE isodecylalcohol, and POE tridecylalcohol. The

ethoxylated alcohol used in the herbicidal formulations tested in the Examples set forth

herein was BIO-SOFT® N25-7 (POE (7) C12-C15 alcohol, HLB 12.2), available from

Stepan Company. Other suitable examples of ethoxylated alcohols are BIO-SOFT® N, EN,

and E series, and MAKON® DA and TD series, also available from Stepan Company;

BRIJ® 35, 56, and 78, ATLOX® MBA 11/6, 13/5, and 13/20, RENEX® 30, 3 1 and 36, and

SYNPERONIC® A3, A5, A l 1, 91/4 and 91/10, available from Uniqema; GENAPOL® LA

and O series, available from Clariant Corporation; AGNIQUE® FOH series, available from

Cognis Corporation; ETHYLAN® OX 91-8, SN 70, 1204, 048, and 087, available from

Akzo Nobel; and RHODASURF™ DA-530, DA-630, L-4 and RHODASURF™ BC series,

available from Rhodia.

[24] Typical non-limiting examples of POE fatty acid esters include POE dioleate, POE

monolaurate, POE monooleate, POE dioleate, POE monostearate, POE coconut oil fatty acid

ester, and POE tall oil fatty acid ester. The POE fatty acid ester used in the herbicidal

formulations tested in the Examples set forth herein was AGNIQUE® PEG 600ML (POE

monolaurate, where the approximate molecular weight (MW) of the POE group is 600, HLB

14.8), available from Cognis Corporation. Other suitable examples of POE fatty acid esters

are AGNIQUE® 200MO, 400MO, 400 MS, and 660 MS, also available from Cognis

Corporation; MYRJ® 45, 49,51, and 53, available from Uniqema; MAPEG® 200 ML, 400

DO, 400 MO, 400 MOT, and 600 MS, available from BASF Corporation; and STEPAN®

PEG series, available from Stepan Company.

[25] Typical non-limiting examples of alkyl polyglycosides and alkyl polysaccharides

include AGNIQUE® PG 8105-U, AGNIQUE® PG 8107-U, AGNIQUE® PG 8166,

AGNIQUE® PG 9166, and AGNIQUE® PG 266, available from Cognis Corporation;

Triton™ BG-IO and CG-1 10, available from The Dow Chemical Company; and ATPLUS®

438 and 452, available from Uniqema.

[26] Typical non-limiting examples of POE fatty amines include POE tallow amine, POE

cocoamine, POE oleylamine, and POE stearyl amine. Examples of suitable POE fatty amines

are TOXIMUL® TA-2, TA-5, TA-8, TA-IO, and TA-15, available from Stepan Company;

AGNIQUE® CAM-2, CAM-IO, CAM-1 5, CAM-20, OAM-30, TAM-IO, TAM-1 5, TAM-20,

TAM-40, and SAM-50, available from Cognis Corporation; and RHODAMEEN™ PN-430

and RHODAMEEN™ TA-15 available from Rhodia.

[27] Typical non-limiting examples of polymeric surfactants are ATLOX® 4912, 4913,

and 4914, available from Uniqema; and polyvinylpyrrolidone polymers such as AGRIMER

15, 30, and 60, available from International Specialty Products.

[28] Preferred nonionic surfactants include block copolymers of propylene oxide and

ethylene oxide, POE (16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4)

nonylphenol, POE (8) nonylphenol, POE (21)/ POP (4) tristyrylphenol, POE (20) sorbitan

mono-oleate, POE (7) C12-C15 alcohol, and POE monolaurate.

[29] The preferred content of the nonionic surfactant varies depending on whether the

herbicidal composition comprises anionic surfactant. If anionic surfactant is used, the content

of the nonionic surfactant is preferably about 0.2 to 12% by weight, more preferably 0.5 to

8% by weight, most preferably 1 to 5% by weight. If anionic surfactant is not used, the

content of the nonionic surfactant is preferably about 1 to 20% by weight, more preferably 3

to 15% by weight, most preferably 7 to 12% by weight.

Anionic Surfactant

[30] Virtually any agriculturally acceptable anionic surfactant can be added as an optional

component, except that the composition substantially excludes anionic surfactants selected

from the dialkylmetalsulfosuccinates and the metal alkylaromatic sulfonates hi this

embodiment, "substantially excludes" means that such anionic surfactants are not present in

amounts designed to have some advantageous effect (see, e.g., U.S. Pat. No. 5,084,087), as

opposed to being present in trace or minor amounts for no significant practical purpose.

[31] Suitable optional anionic surfactants include but are not limited to ether sulfates and

phosphate esters.

[32] Examples of the ether sulfates include but are not limited to sodium or ammonium

salts of fatty alcohol ether sulfates, sodium or ammonium salts of alkylaryl ether sulfates,

sodium or ammonium salts of ethoxylated alkylaryl ether sulfates, POE tallow amine

alkylphenol ether sulfates, and POE tallow amine alcohol ether sulfate. Commercially

available ether sulfates include SOPROPHOR DSS/15 and 4D 384, available from Rhodia;

WITCOLATE PA, available from Akzo Nobel; AGNIQUE® SNT-45, SLES-270-U, and

SLES-330C, available from Cognis Corporation; and TOXIMUL® TANS-5, TANS-6,

TANS-8, TANS-15, TAAS-5, TAAS-8, TAAS-15, TANS 5B, TANS 8B, and TANS 15B,

available from Stepan Company.

[33] Typical non-limiting examples of the phosphate esters include POE tridecyl ether

phosphate, POE lauryl ether phosphate, POE nonylphenol phosphate, POE isodecyl ether

phosphate, POE dinonylphenol phosphate, and POE 2-ethylhexyl ether phosphate.

Commercially available phosphate esters include RHODAFAC™ BG-510, RE-410, RE-610,

RM-510, RM-710, RS-410, and RS-610, available from Rhodia; ATPHOS™ 3226, 3232,

3250, 3202, 3205, and 3206, available from Uniqema; AGNIQUE® PE 2-EH, PE NP-4, PE

NP6, PE NP-9, PE DNP-8, PE IDA-6, and PE TDA-6, available from Cognis Corporation;

STEPFAC® 8170, 8171, 8172, 8175, 8180, 8181, and 8182, available from Stepan

Company; and PHOSPHOLAN® F546, CS 136, CS 141, and CS 151, available from Akzo

Nobel.

[34] A preferred anionic surfactant is POE (5) tallow amine ether sulfate.

[35] The content of the optional anionic surfactant in the herbicidal composition is

preferably about 0.1 to 5% by weight, more preferably 0.5 to 5% by weight, and most

preferably 1 to 3% by weight.

Hydrocarbon Solvent

[36] The optional hydrocarbon solvent is not restricted so long as it can dissolve the

herbicidal cyclohexanedione oxime compound. Suitable hydrocarbon solvents include but

are not limited to aliphatic hydrocarbon solvents, white spirits and mineral spirits (mixtures

of paraffins, cycloparaffins and aromatic hydrocarbons), and aromatic hydrocarbon solvents.

[37] Typical non-limiting examples of the aliphatic hydrocarbon solvents include

isoparaffinic solvents, normal paraffmic solvents, dearomatized hydrocarbon solvents, and

aliphatic mineral spirits. Commercially available aliphatic hydrocarbon solvents include

pentane; cyclopentane; hexane; heptane; isohexane; isopentane; naphtha; ISOPAR™ M5

L, P, and V, NORP AR™ 12, 13, 14, and 15, and EXXSOL™ D80, D95, DlOO, and D120, all

available from ExxonMobil Chemical; and SHELLSOL™ D40, D60, and D80, and

SHELLSOL™ TD, OMS, TC, TM, all available from Shell Chemicals.

[38] Aromatic hydrocarbon solvents are preferred, and are readily available from a number

of sources. Examples include but are not limited to xylene; phenylxylyl ethane; HISOL®

SAS-296 (a mixture of 1-phenyl- 1-xylylethane and 1-phenyl- 1-ethylphenyl ethane), available

from Nippon Petroleum Company; CACTUS SOLVENT® HP-DMN (containing 80% of

dimethylnaphthalene) and CACTUS SOLVENT® P-IOO (alkylbenzene having carbon

number of 9 to 10), available from Nikko Petrochemical Company; SOLVESSO™ 100, 150,

and 200, AROMATIC 100, 150, and 200, NAPHTHALENE DEPLETED AROMATIC 150

and 200, and ULTRA-LOW NAPHTHALENE AROMATIC 150 and 200 (aromatic

hydrocarbons), available from ExxonMobil Chemical; and HI-SOL® 10 and HI-SOL® 15

(aromatic hydrocarbons), available from Ashland Chemical Company.

[39] Preferred aromatic hydrocarbon solvents are AROMATIC 150 and SOLVESSO™

150, and HI-SOL® 15. AROMATIC 150 was used in the herbicidal formulations tested in

the Examples set forth herein.

[40] The content of the optional hydrocarbon solvent is preferably about 5 to 85% by

weight, and most preferably 5 to 50% by weight.

[41] Further, the herbicidal composition optionally comprises another solvent, and/or

auxiliary components such as antioxidant (e.g., propyl gallate, ascorbyl palmitate, butylated

hydroxytoluene, or butylated hydroxyanisole), thickener, antifoaming agent, perfume,

dyestuff, and emollient (e.g. cetyl alcohol and stearyl alcohol).

[42] Examples of other solvents include but are not limited to 2-ethylhexanol, propylene

glycol, ethylene glycol, diethylene glycol, and glycerin. When 2-ethylhexanol or propylene

glycol is used, the content of the additional solvent in the herbicidal composition is preferably

about 0.5 to 4% by weight.

[43] When the antioxidant propyl gallate is used, the content of the propyl gallate in the

herbicidal composition is preferably about 0.01 to 1% by weight, more preferably 0.05 to

0.5% by weight. Preferred embodiments of the herbicidal composition of the present

invention include 0.2 to 0.3% propyl gallate by weight.

[44] When the emollient cetyl alcohol is used, the content of the cetyl alcohol in the

herbicidal composition is preferably about 0.1 to 5% by weight, more preferably 0.5 to 3% by

weight. Preferred embodiments of the herbicidal composition of the present invention

include 1% cetyl alcohol by weight.

[45] The herbicidal composition of the present invention can be prepared by mixing (a) an

herbicidal cyclohexanedione oxime compound or agriculturally acceptable salt or ester

thereof as an herbicidal ingredient, (b) one or more esters of a fatty acid, (c) one or more

nonionic surfactant, (d) optionally an anionic surfactant that is not a

dialkylmetalsulfosuccinate or a metal alkylaromatic sulfonate, (e) optionally a hydrocarbon

solvent, and optionally other solvents, auxiliaries and so on. There are no specific mixing

condition requirements, and the components do not need to be added in any particular order.

However, when an antioxidant such as propyl gallate is used, it maybe desirable to premix

the antioxidant with the nonionic surfactant(s) or with a mixture of the nonionic surfactant(s)

and the one or more esters of a fatty acid.

[46] The herbicidal compositions of the present invention are typically utilized as

emulsifϊable concentrates, namely they are diluted with water to give an emulsion and applied

to weeds, especially graminaceous weeds such as barnyardgrass (Echinochloa crus-galli),

green foxtail (Setaria viridis), giant foxtail (Setariafaberi), large crabgrass (Digitaria

sanguinalis), annual bluegrass (Poa annuά), blackgrass {Alopecurus myosuroides), oats

(Avena sativά), wild oats (Avenafatu ά), johnsongrass (Sorghum halepense), quackgrass

(Agropyron repens), downy brome (Bromus tectorum), and bermudagrass (Cynodon

dactyloή), in broad-leaf crop (e.g. soybean, cotton, sugarbeet, peanut, alfalfa, potatoes, flax,

canola, sunflowers, fruiting vegetables, legume crops, cranberries, cucurbit crops, head and

stem brassica crops, leafy brassica crops, lettuce crops, mustard seed, onion, garlic, shallots,

leaks, root vegetables, rhubarb, spinach, strawberry, sweet potato, and many other crops)

fields.

[47] The application dosage is generally about 0.063 to 0.250 pounds active ingredient per

acre (about 70 to 280 grams of active ingredient per hectare) in the amount of the herbicidal

cyclohexanedione oxime compound. One of ordinary skill in the art could determine an

appropriate application dosage, which may vary with crop, objective weeds, weather

conditions and so on. The dilution of the herbicidal composition can be used for aerial

application by helicopter, plane or radio-controlled helicopter.

[48] One of the advantages of the herbicidal composition of the present invention is its

ability to achieve commercially acceptable weed control (>90%) without the need for tank

mixing with crop oil concentrates, crop oil concentrate blends, nonionic surfactant adjuvants,

or ammonium sulfate. However, in certain circumstances, these materials may be desirable

to increase efficacy, or may be required by a tank-mix partner. For example, glyphosate

formulations commonly require the addition of ammonium sulfate. Examples of crop oil

concentrates, crop oil concentrate blends, or nonionic surfactant adjuvants that can be used

with the present invention include AGRI-DEX®, DYNE-AMIC®, and INDUCE®, available

from Helena Chemical Corporation; SILWET® L-77, available from Loveland Industries;

PRIME OIL® and PRIME OIL® EV , DESTINY®, and PREFERENCE®, manufactured by

Agriliance; HERBIMAX® and MSO® CONCENTRATE, manufactured by Loveland

Industries; BRITZ O/S BLEND, manufactured by Britz Fertilizers, Incorporated; and MOR-

ACT®, manufactured by Wilbur-Ellis.

[49] In addition, under practical conditions it can be desirable to mix herbicides to achieve

a broader spectrum of weed control, for example to prevent the need to make two separate

applications of individual herbicides, such as one to control grass weeds and a second to

control broadleaf weeds. However, mixing herbicides can be problematic if there is

antagonism between the active ingredients, between the formulations, or between the

adjuvant recommendations. The present invention overcomes those limitations with respect

to glyphosate formulations, and also with respect to other herbicides such as but not limited

to CADRE® (active ingredient imazapic, available from BASF Corporation), STORM™

(active ingredients acifluorfen and bentazon, available from United Phosphorus,

Incorporated), and COBRA® (active ingredient lactofen, available from Valent U.S.A.

Corporation).

Examples

[50] To illustrate the invention, specific examples are set forth below. These examples are

merely illustrations and are not to be understood as limiting the scope and underlying

principles of the invention in any way. Various modifications of the invention in addition to

those shown and described herein will become apparent to those skilled in the art from the

following examples and foregoing description. Such modifications are also intended to fall

within the scope of the appended claims.

[51] In the following examples, herbicidal formulations of the present invention are tested

for their efficacy against a variety of common weeds hi many cases, comparisons are made

to similar commercially available herbicidal formulations which contain clethodim as the

active ingredient. One such commercially available herbicidal formulation used for

comparison purposes is SELECT® 2 EC, a product of Valent U.S.A. Corporation.

[52] In all the tables showing efficacy of the herbicidal formulations against various

species of weeds, the numerical values represent the percentage of weed control, or percent

kill of the various species. The use rate of the herbicidal formulations is expressed in terms

of pounds of active ingredient per acre (Ib ai/A).

[53] Several herbicidal formulations of the present invention were tested in the following

examples. These herbicidal formulations are defined as follows:

Formulation I

% bv weight

Clethodim Technical 13.2

C16-Cl 8 fatty acid methyl esters 77.75

POE(5) tallow amine ether sulfate 1.65

POE(1 6) castor oil 1.35

Cetyl alcohol 1.0

Propyl gallate 0.25

AROMATIC 150 balance

Formulation J

% bv weight





POE(30) castor oil 1.2

Propyl gallate 0.3


Formulation K

% bv weight





POE(30) castor oil 0.45

Propyl gallate 0.3


Formulation L

% by weight


C16-C18 fatty acid methyl esters 65.0

P0E(5) tallow amine ether sulfate 1.5



Formulation M

% by weisht


C16-Cl 8 fatty acid methyl esters 40

POE (40) castor oil 5

EO-PO block copolymer, avg. MW 3650 5


Formulation N

% by weight





Formulation O

% by weight



POE (4) nonylphenol 5

POE (8) nonylphenol 5


Formulation P

% by weight



POE (21)/P0P (4) tristyrylphenol 4



Formulation Q

% by weight



POE (20) sorbitan mono-oleate 10


Formulation R

% by weight




POE (7) C12-C15 alcohol 5


Formulation S

% bv weight




POE (approx. MW 600) monolaurate 5


Example 1

[54] Several formulations of the present invention were tested for chemical stability. Table

I illustrates that the enhanced clethodim formulations of the present invention are storage

stable for extended periods.

[55] Materials and Methods: Several formulations were tested for stability of the active

ingredient over various time periods at 400C or at room temperature. The percent clethodim

remaining was calculated based on a starting clethodim value of 100%.

[56] Results and Discussion: The chemical stability results are indicated in the following

Table I. The chemical stability of formulations containing clethodim is an important

consideration, since many standard adjuvant materials and surfactants, including anionic

surfactants such as calcium DDBS, are known in the art to cause rapid degradation of

clethodim and other cyclohexanedione oximes. Yet the results show that these formulations

are unexpectedly stable over extended periods of time.

Table I

[57] Significance: Addition of many types of adjuvant materials and surfactants, including

anionic surfactants such as ether sulfates, to formulations of clethodim and other

cyclohexanedione oximes can cause rapid degradation of the active ingredient. The

formulations of the present invention contain significant amounts of a fatty acid methyl ester

adjuvant and POE(5) tallow amine ether sulfate and yet are chemically stable over extended

periods of time.

Example 2

[58] The control of ROUNDUP READY® corn at 7 and 2 1 days after treatment (DAT)

was compared for the herbicidal formulations of the present invention and SELECT® 2 EC,

where ammonium sulfate was added to the formulations. Ammonium sulfate is commonly

used and often required as a tank mix adjuvant with glyphosate to increase efficacy. The

results presented in Table II show that the formulations of the present invention demonstrate

increased speed of control, resulting in more rapid herbicide symptoms in susceptible weed

species under these conditions.

[59] Materials & Methods-General Application: ROUNDUP READY® corn was used in

this experiment as the target weed species. A single application was made to actively

growing corn which had reached 12 to 24 inches in height. All herbicide treatments included

ammonium sulfate at 2.5 lbs per acre and were made using identical equipment and

application methods.

[60] Results & Discussion: At 7 and 2 1 days after application the treatments containing

Formulations M, N, O, P, Q, R, and S resulted in quicker and more complete grass control

compared to the commercial SELECT® 2 EC formulation. Detailed data are contained in the

following table:

Table II

[61] Significance of Invention: Clethodim is known to provide excellent control of a wide

array of grassy weeds; however the speed of visual activity generally requires up to 10 days.

The clethodim formulations of the present invention provide much quicker visual control

symptoms than SELECT® 2 EC, providing the user with assurance that the product is

working.

Example 3

[62] The control of a number of susceptible weed species at 14 and 28 days after treatment

(DAT) was compared for the herbicidal formulations of the present invention and SELECT 2

EC. The results presented in Tables III and IV show that the clethodim formulations of the

present invention are superior to SELECT® 2 EC because, at lower amounts of active

ingredient per acre, the inventive formulations achieve at least equivalent, and in many cases

more complete, control of susceptible weed species.

[63] Materials & Methods-General Application: Giant Foxtail (Setariafaberi), Yellow

Foxtail (Setaria glauca), Fall Panicum (Panicum dichotomiflorum), Barnyardgrass

(Echinochola crusgalli), Large Crabgrass (Digitaria sanquinalis), and ROUNDUP READY®

Corn (Zea mays) were used as the target weed species in this example. Applications were

made to actively growing weeds with a backpack sprayer using 15 gallons of water per acre.

All herbicide treatments included ammonium sulfate at 2.5 Ib per acre and were made using

identical equipment and application methods.

[64] Results & Discussion: At 14 and 28 days after application, the treatments containing

Formulations J, K and L at 0.063 Ib ai/A resulted in quicker and more complete grass control

compared to the commercial SELECT® 2 EC formulation at 0.078 Ib ai/A. Formulations J, K

and L applied at 0.100 Ib ai/A resulted in at least equivalent, and in many cases more

complete, grass control compared to the commercial SELECT® 2 EC formulation applied at

0.125 Ib ai/A. Detailed data are contained in the following tables:

Table III

[65] Significance of Invention: The clethodim formulations of the present invention are

superior to SELECT® 2 EC, because they can be used at 80% or less of the amount of active

ingredient per acre and achieve at least equivalent, and in many cases more complete, control

of susceptible weeds species.

Example 4

[66] Table V illustrates that the enhanced clethodim formulations of the present invention

are superior to SELECT® 2 EC because they do not require a crop oil concentrate (COC)

adjuvant to provide commercially acceptable efficacy.

[67] Materials & Methods-General Application: ROUNDUP READY® corn was used in

this experiment as the target weed species. A single application was made to actively

growing corn using 20 gallons of water per acre and applied with a tractor-mounted sprayer.

The SELECT® 2 EC treatments all contained COC at 25.6 oz/A. The treatments using

Formulations I, K, and L of the present invention contained a nonionic surfactant (NIS) at 6.4

oz/A, but did not contain any COC. All herbicide treatments included ammonium sulfate at

3.4 lbs per acre and were made using identical equipment and application methods.

[68] Results & Discussion: At 7, 14 and 2 1 days after application, the treatments

containing Formulations I, K and L resulted in at least equivalent, and in some cases more

complete, grass control compared to the commercial SELECT® 2 EC formulation plus COC

at essentially equivalent amounts of active ingredient per acre. Detailed data are contained in

the following table:

Table V

[69] Significance of Invention: Clethodim is known to provide excellent control of a wide

array of grassy weeds; however, the effectiveness of clethodim is generally dependent on the

addition of a COC adjuvant, which may not always be a desirable addition to the spray

program, and is in fact prohibited on many glyphosate labels. The clethodim formulations of

the present invention provide equivalent or better efficacy compared to SELECT® 2 EC

without the addition of a COC adjuvant.

We claim:

1. An herbicidal composition comprising:

(a) an effective amount of an herbicidal cyclohexanedione oxime compound or

agriculturally acceptable salt or ester thereof;

(b) one or more esters of a fatty acid; and

(c) one or more nonionic surfactant;

wherein said composition substantially excludes anionic surfactants selected from the group

consisting of: the dialkylmetalsulfosuccinates and the metal alkylaromatic sulfonates.

2. The herbicidal composition of claim 1 comprising:

(a) about 1 to 40% by weight of said herbicidal cyclohexanedione oxime compound

or agriculturally acceptable salt or ester thereof;

(b) about 10 to 90% by weight of said one or more esters of a fatty acid; and

(c) about 1 to 20% by weight of said one or more nonionic surfactant.





(c) about 1 to 20 % by weight of said one or more nonionic surfactant;

wherein said herbicidal composition further comprises:

(d) about 5 to 85% by weight of a hydrocarbon solvent.





(c) about 0.2 to 12% by weight of said one or more nonionic surfactant;


(d) about 0.1 to 5% by weight of an anionic surfactant other than a

dialkylmetalsulfosuccinate or a metal alkylaromatic sulfonate.




(b) about 10 to 90% by weight of said one or more esters of a fatty acid;

(c) about 0.2 to 12% by weight of said one or more nonionic surfactant; and

(d) about 0.1 to 5% by weight of an anionic surfactant other than

dialkylmetalsulfosuccinates and the metal alkylaromatic sulfonates;


(e) about 5 to 85% by weight of a hydrocarbon solvent.

6 . The herbicidal composition of any one of claims 1 to 5, wherein said herbicidal

cyclohexanedione oxime compound is clethodim, sethoxydim, alloxydim, cycloxydim,

butroxydim, tralkoxydim, tepraloxydim, or profoxydim.

7. The herbicidal composition of claim 6, wherein said herbicidal cyclohexanedione

oxime compound is clethodim or sethoxydim.

8. The herbicidal composition of claim 7, wherein said herbicidal cyclohexanedione

oxime compound is clethodim.

9. The herbicidal composition of any one of claims 1 to 5, comprising 3 to 30% by

weight of said herbicidal cyclohexanedione oxime compound or agriculturally acceptable salt

or ester thereof.

10. The herbicidal composition of claim 9, comprising 10 to 30% by weight of said

herbicidal cyclohexanedione oxime compound or agriculturally acceptable salt or ester

thereof.

11. The herbicidal composition of any one of claims 1 to 5, wherein said esters of a fatty

acid are C1-C8 alkyl esters of C12-C22 organic monobasic acids.

12. The herbicidal composition of claim 11, wherein said esters of a fatty acid are methyl

oleate, methyl palmitate, isopropyl myristate, octyl laurate, isopropyl palmitate, butyl

stearate, or mixtures thereof.

13. The herbicidal composition of claim 12, wherein said esters of a fatty acid are

predominantly a mixture of the methyl esters of C16-C18 fatty acids.

14. The herbicidal composition of any one of claims 1 to 5, comprising 20 to 80% by

weight of said esters of a fatty acid.


esters of a fatty acid.

16. The herbicidal composition of any one of claims 1 to 5, wherein said nonionic

surfactant comprises one or more nonionic surfactants selected from the group consisting of:

polyoxyethylene (POE) derivatives of tallow or plant oils, POE sorbitan esters, ethylene

oxide-propylene oxide (EO-PO) block polymers, POE alkylphenols, polyoxyalkylene

polyarylethers, ethoxylated alcohols, POE fatty acid esters, alkyl polyglycosides and

alkylpolysaccharides, POE fatty amines, and polymeric surfactants.

17. The herbicidal composition of claim 16, wherein said nonionic surfactant comprises

one or more nonionic surfactants selected from the group consisting of: POE (16) castor oil,

POE (30) castor oil, POE (40) castor oil, POE (4) nonylphenol, POE (8) nonylphenol, POE

(21)/ POP (4) tristyrylphenol, POE (20) sorbitan mono-oleate, POE (7) C12-Cl 5 alcohol, and

POE monolaurate.

18. The herbicidal composition of claim 1, 2, or 3, comprising 3 to 15 % of said nonionic

surfactant.

19. The herbicidal composition of claim 18, comprising 7 to 12% of said nonionic

surfactant.

20. The herbicidal composition of claim 1, 4, or 5, comprising 0.5 to 8% of said nonionic

surfactant.

2 1. The herbicidal composition of claim 20, comprising 1 to 5% of said nonionic

surfactant.

22. The herbicidal composition of claim 4 or 5, wherein said anionic surfactant is selected

from the group consisting of: ether sulfates and phosphate esters.

23. The herbicidal composition of claim 22, wherein said anionic surfactant is POE (5)

tallow amine ether sulfate.

24. The herbicidal composition of claim 4 or 5, comprising 0.5 to 5% by weight of said

anionic surfactant.

25. The herbicidal composition of claim 24, comprising 1 to 3 % of said anionic

surfactant.

26. The herbicidal composition of claims 3 or 5, comprising 5 to 50% by weight of said

hydrocarbon solvent.

27. The herbicidal composition of any one of claims 1 to 5, further comprising one or

more additional solvents.

28. The herbicidal composition of claim 27, wherein said one or more additional solvent

is selected from the group consisting of: 2-ethylhexanol, propylene glycol, ethylene glycol,

diethylene glycol, and glycerin.

29. The herbicidal composition of claim 27, wherein said one or more additional solvent

is selected from the group consisting of: 2-ethylhexanol and propylene glycol.

30. The herbicidal composition of claim 29, comprising 0.5 to 4% by weight of said 2-

ethylhexanol and/or propylene glycol.

31. The herbicidal composition of any one of claims 1 to 5, further comprising one or

more antioxidants, thickeners, antifoaming agents, perfumes, dyestuffs, and/or emollients.

32. The herbicidal composition of claim 31, wherein said antioxidant is propyl gallate,

ascorbyl palmitate, butylated hydroxytoluene, and/or butylated hydroxyanisole.

33. The herbicidal composition of claim 32, wherein said antioxidant is propyl gallate.

34. The herbicidal composition of claim 33, comprising about 0.01 to 1% by weight of

said propyl gallate.

35. The herbicidal composition of claim 34, comprising 0.05 to 0.5% by weight of said

propyl gallate.

36. The herbicidal composition of claim 31, wherein said emollient is selected from the

group consisting of: cetyl alcohol and stearyl alcohol.

37. The herbicidal composition of claim 36, wherein said emollient is cetyl alcohol.

38. The herbicidal composition of claim 37, comprising about 0.1 to 5% by weight of said

cetyl alcohol.

39. The herbicidal composition of claim 38, comprising 0.5 to 3% by weight of said cetyl

alcohol.

40. The herbicidal composition of claim 1, 2, or 3, wherein said herbicidal

cyclohexanedione oxime compound is clethodim; said esters of a fatty acid are predominantly

a mixture of the methyl esters of C16-Cl 8 fatty acids; and said nonionic surfactant is selected

from the group consisting of: block copolymers of propylene oxide and ethylene oxide, POE

(16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4) nonylphenol, POE (8)

nonylphenol, POE (21)/ POP (4) tristyrylphenol, POE (20) sorbitan mono-oleate, POE (7)

C12-Cl 5 alcohol, and POE monolaurate.

4 1. The herbicidal composition of claim 40, comprising 10 to 30% by weight of said

clethodim; 30 to 80% by weight of said mixture of the methyl esters of C16-C18 fatty acids;

and 7 to 12% by weight of said nonionic surfactant.

42. The herbicidal composition of claims 4 1, further comprising 5 to 50% by weight of an

aromatic hydrocarbon solvent.

43. The herbicidal composition of claim 1, 4, or 5, wherein said herbicidal

cyclohexanedione oxime compound is clethodim; said esters of a fatty acid are predominantly

a mixture of the methyl esters of C16-Cl 8 fatty acids; and said nonionic surfactant is selected

from the group consisting of: block copolymers of propylene oxide and ethylene oxide, POE

(16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4) nonylphenol, POE (8)

nonylphenol, POE (21)/ POP (4) tristyrylphenol, POE (20) sorbitan mono-oleate, POE (7)

C12-C15 alcohol, and POE monolaurate.


clethodim; 30 to 80% by weight of said mixture of the methyl esters of C16-Cl 8 fatty acids;

and 1 to 5% by weight of said nonionic surfactant; further comprising 1 to 3% by weight of

POE (5) tallow amine ether sulfate.

45. The herbicidal composition of claim 44, further comprising 5 to 50% by weight of an

aromatic hydrocarbon solvent.

46. The herbicidal composition of any one of claims 1 to 5, wherein the ratio of said

esters of a fatty acid to said cyclohexanedione oxime compound is 0.5:1 to 25:1 by weight.

47. The herbicidal composition of claim 46, wherein the ratio of said esters of a fatty acid

to said cyclohexanedione oxime compound is 0.8:1 to 12:1 by weight.

48. The herbicidal composition of claim 47, wherein the ratio of said esters of a fatty acid

to said cyclohexanedione oxime compound is 1:1 to 6:1 by weight.

49. A method for controlling the growth of vegetation comprising applying to said

vegetation an herbicidally-effective amount of an herbicidal composition comprising:

(a) an effective amount of an herbicidal cyclohexanedione oxime compound or

agriculturally acceptable salt or ester thereof;

(b) one or more esters of a fatty acid; and

(c) one or more nonionic surfactant;

wherein said herbicidal composition substantially excludes anionic surfactants selected from

the group consisting of: the dialkylmetalsulfosuccinates and the metal alkylaromatic

sulfonates.

50. The method of claim 49, wherein said herbicidal composition comprises:




(c) about 1 to 20% by weight of said one or more nonionic surfactant.





(c) about 1 to 20% by weight of said one or more nonionic surfactant;


(d) about 5 to 85% by weight of a hydrocarbon solvent.





(c) about 0.2 to 12% by weight of said one or more nonionic surfactant;


(d) about 0.1 to 5% by weight of an anionic surfactant other than a

dialkylmetalsulfosuccinate or a metal alkylaromatic sulfonate.





(c) about 0.2 to 12% by weight of said one or more nonionic surfactant; and

(d) about 0.1 to 5% by weight of said anionic surfactant other than a

dialkylmetalsulfosuccinate or a metal alkylaromatic sulfonate;


(e) about 5 to 85% by weight of a hydrocarbon solvent.

54. The method of any one of claims 49 to 53, wherein said vegetation is a grass plant.

55. The method of claim 54, wherein said grass plant is in a post-emergence growth stage.

56. The method of any one of claims 49 to 53, wherein said herbicidal cyclohexanedione

oxime compound is clethodim, sethoxydim, alloxydim, cycloxydim, butroxydim,

tralkoxydim, tepraloxydim, or profoxydim.

57. The method of claim 56, wherein said herbicidal cyclohexanedione oxime compound

is clethodim or sethoxydim.

58. The method of claim 57, wherein said herbicidal cyclohexanedione oxime compound

is clethodim.

59. The method of any one of claims 49 to 53, wherein said herbicidal composition

comprises 3 to 30% by weight of said herbicidal cyclohexanedione oxime compound or

agriculturally acceptable salt or ester thereof.

60. The method of claim 59, wherein said herbicidal composition comprises 10 to 30% by

weight of said herbicidal cyclohexanedione oxime compound or agriculturally acceptable salt

or ester thereof.

61. The method of any one of claims 49 to 53, wherein said esters of a fatty acid are C1-

C8 alkyl esters of C12-C22 organic monobasic acids.

62. The method of claim 6 1, wherein said esters of a fatty acid are methyl oleate, methyl

palmitate, isopropyl myristate, octyl laurate, isopropyl palmitate, butyl stearate, or mixtures

thereof.

63 . The method of claim 6 1, wherein said esters of a fatty acid are predominantly a

mixture of methyl esters of C16-Cl 8 fatty acids.


comprises 20 to 80% by weight of said esters of a fatty acid.


weight of said esters of a fatty acid.

66. The method of any one of claims 49 to 53, wherein said nonionic surfactant comprises

one or more nonionic surfactants selected from the group consisting of: polyoxyethylene

(POE) derivatives of tallow or plant oils, POE sorbitan esters, ethylene oxide-propylene oxide

(EO-PO) block polymers, POE alkylphenols, polyoxyalkylene polyarylethers, ethoxylated

alcohols, POE fatty acid esters, alkyl polyglycosides and alkylpolysaccharides, POE fatty

amines, and polymeric surfactants.

67. The method of claim 66, wherein said nonionic surfactant is selected from the group

consisting of: POE (16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4)


mono-oleate, POE (7) C12-Cl 5 alcohol, and POE monolaurate.

68. The method of claim 49, 50, or 51, wherein said herbicidal composition comprises 3

to 15% by weight of said nonionic surfactant.


weight of said nonionic surfactant.

70. The method of claim 49, 52, or 53, wherein said herbicidal composition comprises 0.5

to 8% by weight of said nonionic surfactant.

7 1. The method of claim 70, wherein said herbicidal composition comprises 1 to 5% by

weight of said nonionic surfactant.

72. The herbicidal composition of claim 52 or 53, wherein said anionic surfactant is

selected from the group consisting of: ether sulfates and phosphate esters.

73. The herbicidal composition of claim 72, wherein said anionic surfactant is POE (5)

tallow amine ether sulfate.

74. The method of claim 52 or 53, wherein said herbicidal composition comprises 0.5 to

5% by weight of said anionic surfactant.


weight of said anionic surfactant.

76. The method of claim 5 1 or 53, wherein said herbicidal composition comprises 5 to

50% by weight of said hydrocarbon solvent.


further comprises one or more additional solvents.

78. The method of claim 77, wherein said one or more additional solvent is selected from

the group consisting of: 2-ethylhexanol, propylene glycol, ethylene glycol, diethylene glycol,

and glycerin.

79. The method of claim 78, wherein said one or more additional solvent is selected from

the group consisting of: 2-ethylhexanol and propylene glycol.

80. The method of claim 79, wherein said herbicidal composition comprises 0.5 to 4% by

weight of said 2-ethylhexanol and/or propylene glycol.


further comprises one or more antioxidants, thickeners, antifoaming agents, perfumes,

dyestuffs, and/or emollients.

82. The method of claim 81, wherein said antioxidant is propyl gallate, ascorbyl

palmitate, butylated hydroxytoluene, and/or butylated hydroxyanisole.

83. The method of claim 82, wherein said antioxidant is propyl gallate.

84. The method of claim 83, wherein said herbicidal composition comprises about 0.01 to

1% by weight of said propyl gallate.

85. The method of claim 84, wherein herbicidal composition comprises 0.05 to 0.5% by

weight of said propyl gallate.

86. The herbicidal composition of claim 81, wherein said emollient is selected from the

group consisting of: cetyl alcohol and stearyl alcohol.

87. The method of claim 86, wherein said emollient is cetyl alcohol.

88. The method of claim 87, wherein said herbicidal composition comprises about 0.1 to

5% by weight of said cetyl alcohol.

89. The method of claim 88, wherein said herbicidal composition comprises 0.5 to 3% by

weight of said cetyl alcohol.

90. The method of claim 49, 50, or 51, wherein said herbicidal cyclohexanedione oxime

compound is clethodim; said esters of a fatty acid are predominantly a mixture of the methyl

esters of C16-C18 fatty acids; and said nonionic surfactant is selected from the group

consisting of: block copolymers of propylene oxide and ethylene oxide, POE (5) tallow

amine ether sulfate, POE (16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4)




weight of said clethodim; 30 to 80% by weight of said mixture of the methyl esters of Cl 6-

Cl 8 fatty acids; and 7 to 12% by weight of said nonionic surfactant.

92. The method of claim 91, wherein said herbicidal composition further comprises 5 to

50% by weight of an aromatic hydrocarbon solvent.

93. The method of claim 49, 52, or 53, wherein said herbicidal cyclohexanedione oxime

compound is clethodim; said esters of a fatty acid are predominantly a mixture of the methyl

esters of C16-Cl 8 fatty acids; and said nonionic surfactant is selected from the group

consisting of: block copolymers of propylene oxide and ethylene oxide, POE (5) tallow

amine ether sulfate, POE (16) castor oil, POE (30) castor oil, POE (40) castor oil, POE (4)




weight of said clethodim; 30 to 80% by weight of said mixture of the methyl esters of C16-

Cl 8 fatty acids; and 1 to 5% by weight of said nonionic surfactant; further comprising 1 to

3% of POE (5) tallow amine ether sulfate.

95. The method of claim 94, wherein said herbicidal composition further comprises 5 to

50% by weight of an aromatic hydrocarbon solvent.

96. The method of any one of claims 49 to 53, wherein the ratio of said esters of a fatty

acid to said cyclohexanedione oxime compound is 0.5:1 to 25:1 by weight.

97. The method of claim 96, wherein the ratio of said esters of a fatty acid to said

cyclohexanedione oxime compound is 0.8:1 to 12:1 by weight.

98. The method of claim 97, wherein the ratio of said esters of a fatty acid to said

cyclohexanedione oxime compound is 1:1 to 6:1 by weight.

99. The method of any one of claims 49 to 53, wherein said herbicidal composition is

applied at an application dosage rate of about 0.063 to 0.250 pounds active ingredient per

acre.


applied to said vegetation without the addition of adjuvants selected from the group

consisting of: ammonium sulfate, crop oil concentrates, crop oil concentrate blends, and

nonionic surfactant adjuvants.


tank mixed with one or more other biologically active chemicals before said applying to said

vegetation.

102. The method of claim 101, wherein said one or more biologically active chemicals is

selected from the group consisting of: herbicides, insecticides, and fungicides.

103. The method of claim 101, wherein said one or more other biologically active

chemicals is selected from the group consisting of: glyphosate, lactofen, imazapic,

acifluorfen, bentazone, and pyrithiobac-sodium.

International application NoINTERNATIONAL SEARCH REPORT

PCT7US05/39443

A CLASSIFICATION OF SUBJECT MATTEREPC AOlN 25/30( 2006 01),35/10( 2006 01),37/36( 2006 01),43/14( 2006 01),A01P 13/00( 2006 01)

USPC 504/288,292,315,343According to International Patent Classification (IPC) or to both national classification and IPC

FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols)U S 504/288, 292, 315, 343

Documentation searched other than minimum documentation to the extent that such documents are included m the fields searchedNONE

Electronic data base consulted duπng the international search (name of data base and, where practicable, search terms used)Please See Continuation Sheet

DOCUMENTS CONSIDERED TO BE RELEVANT

Category : Citation of document, with indication, where appropπate, of the relevant passages Relevant to claim No

US 2004/001 8940 Al (HACKER et al) 29 January 2004 See abstract, paragraphs 68-107 1-103

Further documents are listed in the continuation of Box C See patent family annex

* Special categories of cited documents T later document published after the international filing date or prioritydate and not in conflict with the application but cited to understand the

"A" document defining the general state of the art which is not considered to be of principle or theory underlying the inventionparticular relevance

"X ' document of particular relevance, the claimed invention cannot beE' earlier application or patent published on or after the international filing date considered novel or cannot be considered to involve an inventive step

when the document is taken alone"L" document which may throw doubts on priority claim(s) or which is cited to

establish the publication date of another citation or other special reason (as ' Y" document of particular relevance, the claimed invention cannot bespecified) considered to involve an inventive step when the document is

combined with one or more other such documents, such combination' O" document referring to an oral disclosure, use, exhibition or other means being obvious to a person skilled in the art

P ' document published prior to the international filing date but later than the "& ' document member of the same patent famil>priority date claimed

Date of the actual completion of the international search Date of

14 March 2006 (14.03 2006)Name and mailing address of the ISA/US

Mail Stop PCT, Attn ISA/USCommissioner For Patents S

P O Box 1450Alexandria, Virginia 22313-1450 Telephone No 571-272-1600

Facsimile No (571) 273-3201

Form PCT/ISA/210 (second sheet) (Apπl 2005)

International application No.INTERNATIONAL SEARCH REPORT PCTΛJS05/39443

Continuation of B. FIELDS SEARCHED Item 3 :WEST: cyclohex-, dione-, clethodim, sethoxydim, alloxydim, cycloxydim, butroxydim, tralkoxydim, tepraloxydim, profoxydim, -oxydim,fatty etc. with ester-, surfact-

Form PCT/ISA/210 (extra sheet) (April 2005)

WO 2007/050090 Al

Documents

Transcript of WO 2007/050090 Al