AU614730B2 - Compositions including herbicidal combinations of the glyphosate type and the phenoxybenzoic type - Google Patents

Abstract

Herbicidal composition comprising at least one herbicide of the glyphosate type and at leat one herbicide of the phenoxybenzoic type, preferably acifluorfen sodium, the weight ratio between the phenoxybenzoic herbicide and the glyphosate herbicide being comprised between 1/12 and 1/80, preferably between 1/15 and 1/50. This composition is particularly resistant to washing due to precipitations which occur just after application.

Description

'ATEN OFCEA.C

PCT

0OPI DATE 23/05/89 AOJP DATE 29/06/89 APPLN. I D 81788 87 PCT NUMBER PCT/FR87/00423 DEMANDE INTERNATIONALE I~nLLz,I I~a AsL -nnWii -I'M I~,sj I~sn 1a n-t1z.t U, i.x 1 PClIT (51) Classification internationale des brevets 4 nmeroje puffi7a timoter jnale: WO 89/ 03641 AO1N 41:0,5739:02) (AOLN 57/2 A AOIN 57/208, (AO1N 57/20 Al e d 3icion i eataIe: 5 mai 1989 (05.05.89) A01N 41:08, 39:02) 0 t (21) Numnro de la demande internationale: PCT/FR87/00423 JP, KR, LU (brevet europ~en), ML (brevet OAPI), MR (brevet OAPI), NL (brevet europ~en), RO, SD, (22) Date de d~p6t international: 28 octobre 1,87 (28.10.87) SE (brevet europ~en), SN (brevet QAPI), SU, TD (brevet QAPI), TG (brevet OAPI).

(71) D36posant: RHONE-POULENC AGROCHIMIE [FR/ FR]; 14-20, rue Pierre-Baizet. F-69009 Lyon Publike (72) Inventeurs: DECOR, Jean-Pierre Chemin de la Croix- vcrpotdrehceinrainl.

Blanche, Soucieu-en-Jarret, F-69510 Thurins (FR).

BORROD, Guy 38 bis, rue des Granges, F-69005 Lyon (FR).

(74) Mandataire: RANGUIS, Patrick; Rh6ne-Poulenc Agrochimie, DPI, BP 9163, F-69263 Lyon C~dex 09

(FR).

(81) Etats d~sign~s: AT (brevet europ~en), AU, BE (brevet europ~en), BG, BJ (brevet OAPI), BR, CF (brevet QAPI), CG (brevet QAPI), CH (brevet europ~en), CM (brevet QAPI), DE (brevet europ~en), DK, Fl, FR.

(brevet europ~en), GA (brevet OAPI), GB (brevet europ~en), HU, IT (brevet europ~en), (54) Title: COMPOSITIONS INCLUDING HERBICIDAL COMBINATIONS OF THE GLYPHOSATE TYPE AND THE PHENOXYBENZOIC TYPE (54)Titre: COMPOSITIONS COMPRENANT DES COMBINAISONS D'HERBICIDES DE TYPE GLYPHOSATE ET DE TYPE PHENOXYB1FNZOIQUE (57) Abstract Herbicidal composition comprising at least one herbicide of the glyphosate type and at leat one herbicide of the phenoxybenzoic type, preferably acifluorfen sodium, the weight ratio between the phenoxybenzoic herbicide and the glyphosate herbicide being comprised between 1/12 and 1/80, preferably between 1/15 and 1/50. This composition is particularly resistant to washing due to precipitations which occur just after application.

(57) Abr~g6 Composition herbicide comprenant au momns un herbicide de type glyphosate et au momns un herbicide de type ph6noxybenzoifque, de pr~f~rence l'acifluorfensodium, le rapport pond~ral herbicide de type ph~noxybenzoYque/herbicide de, type glyphosate 6tant compris entre 1/12 et 1/80, de pr~f~rence entre 1/15 et 1/50. Cette composition est notamnment r~sistante au lessivage lors des pr~cipitations qui se produisent peu de temps apr~s I'application.

I

I

I I VERIbED TRANSLAflOQN U- V 1 a "Herbicidal compositions based on a glyphosate type herbicide and a phenoxybenzoic type herbicide and method for the treatment of undesirable plants using these compositions".

The present invention relates to new herbicidal compositions based on a glyphosate type herbicide and a phenoxybenzoic type herbicide. It also relates to a method for the treatment of undesirable plants using these compositions. Glyphosate (or N-phosphonomethylglycine) and its salts are well known wide spectrum herbicides which are active against annual and perennial weeds. This class of herbicides is especially known for its post-emergence efficacy and is used for agricultural applications and for garden activities. Nevertheless, it is still desirable to improve the herbicidal activity of these compounds.

However, it is known that glyphosate type herbicides act relatively slowly. In fact, a period of approximately three weeks is generally required to observe the effects.

In order to overcome this disadvantage, the PCT Patent Application WO 84/03,607 indicates that in the specific case of application to amateur gardens, the addition of a certain quantity of acifluorfen or one of its i salts to glyphosate type herbicides increases the speed of action of glyphosate type herbicides. In this context, an I effective quantity of glyphosate type herbicide is employed S and acifluorfen is added so that the ratio by weight is l c 2 practically between 1:8.33 and 4.2. However, it is observed that the compositions described reveal a marked antagonism in many cases, which results in the efficacy of the glyphosate type herbicide being adversely affected. The use of extemporaneous mixtures of glyphosate and acifluorfen against weeds of field crops such as soyabean, and not of garden weeds, has also been proposed. Thus, the publication: Proceedings, Southern Weed Science Society, 38th annual meeting, Sanberg et al., 1985, pages 86 to 89, indicates that r 430 g/ha dose of glyphosate combined with g/ha of acifluorfen shows a marked antagonism against the weeds tested, this antagonism decreasing, moreover, when the glyphosate:acifluorfen ratio decreases, i.e. when the quantity of acifluorfen is increased.

A second publication, Ibid, pages 64-67, Frost et al., also confirms the fact that it is necessary to increase the dose of acifluorfen.

It is also seen from the latter publication that the spectrum of activity of glyphosate is reduced, especially against graminaceous plants.

Another disadvantage related to the mode of action of glyphosate or of its derivatives lies in the fact that it can very easily be washed out, i.e. if there is a heavy rainfall a few hours after its application, a large part of it is removed. It is also desirable to improve the action of glyphosate type herbicides on plants whose growth is slowed down by low temperatures and/or a low humidity, r

I

:i

I

:1 i

I

1 ~tQ

I;

i 1 tr( I i; r ii iii 3 or on plants which are at the end of their growth cycle.

In an unexpected way, the present invention enables these disadvantages to be overcome and more particularly, it enables one or more of the following objects to be achieved: to increase the speed of action of glyphosate type herbicides; to improve the activity spectrum of glyphosate type herbicides; to improve the herbicidal properties of glyphosate type herbicides; to prevent glyphosate type herbicides from being washed out; and to improve the activity of glyphosate type herbicides on plants whose growth is slowed down by low temperatures and/or a low humidity or on plants which are at the end of their growth cycle.

According to the present invention, the herbicidal composition comprises at least one glyphosate type herbicide and at least one phenoxybenzoic type herbicide (VIII) and is characterized in that the ratio by weight (VIII):(I) is between 1:12 and 1:80 and preferably between 1:15 and 1:50.

This is equivalent to a molar ratio (VIII):(I), taking into account the molar equivalence calculated on the basis of the acid for as well as for (VIII), of 1'I /between 1.2:12 and 1.2:80 and preferably between 1.2:15 rrN 4 -4i and 1.2:50.

DETAILED DESCRIPTION OF THE INVENTION Glyphosate type herbicides The glyphosate type herbicides which may be empLoyed in the present invention are mainly compounds which correspond to formulae I and la below, as well as their metabolites and derivatives. The said compounds are defined by formuLae I and Ia below:

OR

1 O=P-CH -NH-CH 2 -Z (I) 2 2 OR2 in which Z is a cyano group or a group COOR; R is a hydrogen atom, or alternatively, is chosen from amongst lower alkyl, lower alkenyl or lower alkoxyalkyl groups or an aryl group containing 6 to 10 carbon atoms and optionally carrying 1 to 3 substituents chosen independently from lower alkyl, lower alkoxy, halo, trifluoromethyl, nitro and cyano groups or alternatively is a compatible cation which is capable of forming a salt; R and R are identical or different, being hydrogen atoms or being chosen from lower alkyl, aryl, substituted aryl or biphenyl groups, or alternatively, being compatible cations which are capable of forming salts.

3 2- OR I 0 P CH 2 N H CH 2 (Ia) 'A nu l2 OR4 22

R+

T)

i in which

Z

2 is a compatibLe anion, capable of forming a salt;

R

3 and R 4 are identica or different and represent hydrogen atoms or Lower alkyL or aryl groups, which may be substituted, or a biphenyl group; Z is a cyano group or a group COOR 5 5 R may have the same meanings as those given for R, except for the possibility of being a cation.

In formulae I and la, the valued compounds are those in which Z and Z1 are groups COOR and COOR 5 respectively. With regard to formula the valued compounds are those in which R, R and R 2 which may be identical or different, are hydrogen atoms or compatible cations.

Organic salts of ammonium of formula especially those in which R is a cation derived from isopropylamine, give good results and are available on the market. Organic salts of sulphonium or of sulphoxide those in which

R

1 and/or R 2 are the trimethylsulphonium cation or trimethyl sulphoxide) are also suitable. An example of a compound corresponding to formula I or la is the isopropylamine salt of N-(phosphonomethyl)glycine which is the active ingredient in the herbicide marketed by Monsanto under the trade name Roundup.

With regard to formula la, the valued compounds 3 4 are those in which R and R which may be identical or R/AM different, represent lower alkyl or aryl groups, and in Swhich Z1 is a group COOR 5 R being a lower alkyl or "4 -6aryL group.

The cations and anions which are compatible from a herbicidal point of view are cations or anions forming part of a salt of formula I or la which do not alter the herbicidal properties of the compound. The saline form is generally more soluble in water and more advantageous than the free acid or the corresponding free base.

Examples of compatible cations include aLkaLi metal cations such as sodium or potassium; alkaLine earth metal cations such as calcium or magnesium; cations of copper, zinc, iron, nickel, manganese, ammonium or organic ammonium, phosphonium, sulphonium or sulphoxide, these cations preferably having a molecular weight less than 300. The organic cations of ammonium which are suitable include amine derivatives, especially aliphatic, cyclic or heterocyclic amines containing 1 or 2 amine groups, such as alkylamines, alkyleneamines, alkenylamines and alkanolamines. Examples of amine derivatives include, without implied limitation, methylamine, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso-butylamine, sec-butylamine, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonytamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecyLamine, pentadecylamine, hexadecylafiine, heptadecylamine, octadecylamine, methylethylamine, methyliso-propyamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecyl- Samine, ethylbutylamine, ethylheptylamine, ethyLoctylamine, '4 -7 hexyiheptyL amine, hexyLoctylamine, dlimethyamine, diethyLamine, di-n-propyLarnine, di iso-propyLamine, di-n-amyLamine, diiso-amyLamine, dihexyLamine, diheptytamine, dioctyLamine, trimethylamine, triethyLamine, tri-n-propyLamine, tri isopropyLamine, tri-n-butyLamine, tri iso-butyLamine, tri-secbutylamine, tri-n-amyLamine, n-propanoLamine, isopropanoLamine, diethanoLamine, N,N' -diethyLethanoLamine, N-ethylpropanoLamine, N-butyLethanoLamine, aLLyLamine, n-butenyL- 2-ami ne, n-pentenyL-2-amine, 2,3-dimethyLbutenyL-2-amime, dibutenyL-2-amine, n-heyeny1-2-amine and propylenediamine, primary aromatic amines such as aniLine, methoxyaniLine, ethoxyaniLine, ortho-, meta- and para-toLuidine, phenylenedliamine, 2,4,6-tribromoaniline, benzidline, naphthylamine, ortho, meta- and para-chioroaniLine, and the Like; heterocyclic amines such as pyridline, morpholine, piperidline, pyrroLidine, indloLine, azepine and the Like.

Among suitable organic cations of suLphonium and suLphoxidle are Cl-Cl 0 -aLkyL (preferably Cl-C 5 Lower alkyl)suLphonium cations and Cl-Cl 0 -alkyL (preferably Lower alkyL)suLphoxide cations, such as trimethylsuiphonium, ethyLdimethylsuLphonium, tr ipropyLsuLphonium, trimethyl suLphoxidle, triethyl suLphoxidle and the Like. These salts are described in particular in United States of America Patent No. 4,315,765. Suitable phosphonium cations includle, without implied Limitation, those represented by the N formula Ii ffi~-I i.

a b R P RC

I

R"

in which Ra R and R which may be identical or different, represent phenyl or CI to C 10 aLkyL radicals, preferably Lower alkyL. These salts are described in United States of America Patent No. 4,341,549. Other examples of suitable cations are described in United States of America Patent No. 3,799,758. Compatible anions which are suitable include, without implied Limitation, the anions chloride, bromide, fluoride, sulphate, sulphite, bisulphite, phosphate, orthophosphate, carbonate, bicarbonate, acetate, butyrate, benzoate, maleate, and the like.

Compounds of formulae and (la) are described, for example in United States of America Patent Nos.

3,799,758, 3,835,000, 3,950,402, 4,067,719, 4,008,296, 4,147,719 and 4,369,142 which are mentioned in the present specification by way of reference.

A large number of compounds which are metabolized by green plants or which function in a manner equivalent to that of the active part (from a phytotoxic point of view) of glyphosate may also be employed. These compounds include, for example, compounds represented by formulae I and Ia, and by the following formulae.

P- 4 i Ir i i; t -I -e i- 9-

OR'

0- p

OR

OR~

0-?

OR

cli N

Z

R

z

CM

2

NH,

(II)

(Ilb)

OR'

I~P

U 'V

OR

CH' N -CH' z

N-

OR'

CM

2 P -0

OR'

OR'

OR'

OR'

OR-

0P Z 'NH-

OR

-N -Cz -P 0 z OR' -Nu4 0l!

(III)

(IV)

MV

(VI)

OR~

CHz CM, NH, Z R -0O-R' I I 0 P 0- 0 Z- NH lbCM, NH Z

(VII)

I

10 in which:

S

2 R R, R and R have the definitions mentioned above;

Z

4 is a group CH 2 CN; CONHOH (or its tautomeric form -C(OH)=NOH); CH 2 COOR, in which R has the meaning mentioned above; CONR R 8 in which R and R which may be identical or different, also have the same meanings as those given for R; 3 is a group -CH 2 -CN; -CO-NHOH (or its tautomeric form -C(OH)-NOH); -CH 2

-COOR

5 or -CONR 5

R

5 in which the different groups R which may be identical to or different from one another, have one of the meanings mentioned above.

R

50 is a lower alkyl, lower alkoxy, hydroxy, lower alkanoyl, optionally substituted arylcarbonyl, trifluoroacetyl, Lower alkyLthio, Lower alkanoyl; amino, alkylamino, nitro or nitroso group, or a radical -COOR -OCH; COOR 10

-CH

2

P(O)OR

15

(OR

25 -S(O)m-R 1 1

-SO-X-R

1 1 or -CO-S(O)m-R 12 in which R 9 is a lower alkyl, lower alkenyl or optionally 11 substituted aryl group, R is a lower alkyl or optionally substituted aryl group; X represents or x' i is chosen from lower alkyL, lower alkenyl, lower alkynyl, optionally substituted aryl or optionally substituted 15 25 (lower) arylalkyl groups; m is equal to 0, 1 or 2; R15 R 2 and R 10 have the same meanings as those mentioned above for 1 6 l R R is a hydrogen atom or a lower alkyL group; an optiond ally substituted aryl, optionally substituted Lower aryl S or optionally substituted Lower arylalkyl grojp; a group

COOR

5 or 3 in which R, R and R have the definitions mentioned above.

Products of formulae II to VII above are generally known and may be prepared by known methods or methods similar to known m,-thods. These products and methods are described in United States of America Patent Nos. 4,035,177, 4,175,946, 4,251,258, 4,231,782, 4,322,238, 4,322,239, 4,323,387, 4,300,942 and 4,300,943; the United States of America Search Report No. 220,001 (Derwent No. 73,821 United Kingdom latent No. 2,090,596; Belgian Patent No.

888,001; Japanese Patent Nos. 56,139,408, 57,120,595 and 57,099,597; European Publication No. 39,310; and German Federal Republic Patent Application No. 2,361,382. The patents and patent applicaticns mentioned above are mentioned by way of reference.

(Phenoxy-substituted) benzoic derivatives Among (phenoxy-substituted) benzoic derivatives which may be employed in the present invention are compounds which include 2-nitro-5-phenoxy substituted benzoic acids and their derivatives, of formula (VIII) below:

P

VIII

6 -Z

I

Sh Aerica Srepresents a chorine atomr or the group CF 3 A' o 4 •P e o y s b t t t d !ez i e i a i e Amng (peox -sbs iutd)b nz icde iatve and the phenoxybenzoic type herbicide is a cornpound of formula VIII S./3 12 121

Z

5 represents a chlorine or fluorine atom;

Z

7 represents a hydrogen, chlorine or fluorine atom; Z represents a chlorine atom or a nitro group; p has the value 0 or 1;

R

13 and R 14 which may be identical or different, represent hydrogen atoms or methyl groups; 0 Z represents a hydroxy or alkoxy (especially lower alkoxy) or OM (M being an atom of an alkali metal or alkaline earth metal element, more particularly Na or K) or (lower)alkylsulphonamide group.

Among these compounds, compounds of formula VIII 6 8 in which Z is a group C 3 Z is a nitro group, Z 5 is a Cl or I group and Z 7 is a hydrogen atom are preferred, because these more particularly meet the objectives of the present invention Listed in the preamble.

O Among these, the following are preferred: acifluorfen, which is the compound in which p 0 and Z is an OH group, or potassium or sodium salts of acifluorfen (Z 9 OM, M Na or K); fomesafene, which is the compound in which p 0 9 I and Z is N-methylsulphonamide (-NH-S02CH 3 and benzofluorfen, in which p 1, R 1 3 and R 14 H and Z is a group OEt.

Among the latter, acifluorfen-sodium is preferred.

SAccording to the present invention, the new

C,

_y 13 agrochemicaL compositions may contain mixtures of active substances and common ingredients known in practice such as surfactants, carriers and diluents. If the composition contains two substituents, the systemic herbicide and the phenoxybenzoic derivative, or more than two substituents, it is desirable that the compositions mentioned above are suitably mixed, in a homogeneous and/or uniform manner, which mixing can be achieved by means of a particular type of agitation. The compositions may be mixed in a container or premixed, in particuLar premixed.

The present invention also relates to a weed controL method which consists in applying an effective quantity of a herbicidal composition to plants which must be destroyed. This treatment method is destructive in object, and enables, in particular, weed growth to be controlled and where appropriate, the weeds to be destroyed totally or partially.

The herbicidal compositions or mixtures of active substances, as have been described above and which can be used according to the present invention, are applied in a suitable manner to plant Leaves and in particular to weeds to be destroyed, for example when the latter have a green foliage.

The herbicidal compositions may also be applied shortly before the harvest in order to kill weeds having 'fR roots which are persistent in the soil after the harvest.

Thus, it is possible to plant shortLy after the harvest 0

I

14 14 without having to carry out mechanical weeding operations (manuaLLy or otherwise). However, this method is reserved for the cases in which the herbicides applied do not Leave residues and/or are selective towards the crop to be planted after the harvest.

In general, the systemic compound of the glyphosate type is applied to plants at doses from 0.3 to 0.9 kg/ha, preferably from approximately 0.4 to approximately 0.8 kg/ha and especially from approximately 0.5 to approximately 0.7 kg/ha.

Compounds of formula (VIII) are used as chemical substances which modify membranes; a dose which is advantageously between approximately 0.005 and approximately 0.1 kg/ha and preferably between approximately 0.02 and approximately 0.08 kg/ha is applied.

The ratio by weight phenoxybenzoic type herbicide: glyphosate type herbicide is between 1:12 and 1:80 and preferably between 1:15 and 1:50.

Using the compositions of the present invention, an effective control of the following weeds is observed: Dicotyledonous plants: Xanthium, Ipomoea, Sesbania, Abutilon, Polygonum, Amaranthus, Chenopodium, Sinapis, Datura, Solanum, Euphorbia, Bidens and Galinsoga.

Monocotyledonous plants: (graminaceous plants) Setaria, and Echinochloa.

The method according to the present invention makes it possible to control a wide spectrum of effective quantity of glyphosate type herbicide is employed Su and acifLuorfen is added so that the ratio by weight is 15 monocotyLedonous or dicotyledonous annual and perennial weeds. The weeds may be destroyed by the methods and the compositions of the present invention, enabling the field to be Left in a good condition for the subsequent growth of crops such as cereals, wheat, rice, cotton, soyabean, beets (especially sugarbeets), sunflower, rapeseed, sugarcane and vegetable crops, and for achieving an effective weed controL in perennial crops (grape vines and orchards).

As the herbicidal effect appears and becomes effective shortly after treatment [much earlier than with glyphosate type herbicide aLone (when employed in higher 15 doses)], the method and the composition according to the present invention also make it possibLe to control plants, especiaLLy weeds, quickly.

The method according to the present invention also makes it possibLe to prevent glyphosate or its derivatives from being washed out. The invention also relates to a method which makes it possibLe to prevent glyphosate or one of its derivatives of formula mentioned above i' from being washed out, the said method consisting in applying glyphosate or one of its derivatives of formula in combination with a compound of formula (VIII), according to the doses and the ratios by weight defined above.

N) When the method of the present invention is put into practice, the herbicidaL compositions most frequently if< ot it is removed. It is also desirable to improve the /"AL action of glyphosate type herbicides on plants whose growth is slowed down by low temperatures and/or a Low humidity, 16 contain one or more ingredients other than the compounds of glyphosate type and their derivatives (hereinafter referred to as active ingredients). These compositions, 1 which may be employed as herbicidal agents, contain the active ingredients in combination with solid or liquid carriers which are acceptable in agriculture and surfaceactive agents which are acceptable in agriculture. Common inert carriers and common surface-active agents may be employed. These compositions also form part of the present invention.

These compositions may also contain other ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, agents which facilit3.e penetration, activators, stabilizers, sequestering agents and the like, as well as other known active ingredients having pesticidal properties (especially insecticides, fungicides or herbicides) or having plant growth regulating properties. More generally, the compositions employed in the present invention may contain all the solid or liquid additives corresponding to conventional methods of formulation.

In the following description of the present invention, unless otherwise stated, the percentages are expressed on a weight basis.

The activators are compounds which do not normally 16 have herbicidal properties at normat doses (approximately to approximately 5 kg/ha), but which have a capacity Lll 17 i to increase significantly the herbicidaL activity of gLyphosate type compounds. Most of these activators are well known. As described beLow, some activators are surfactants, especially ethylene oxide poLycondensate derivatives of phenol, of aLcohoL or of amines. Some activators are ammonium salts, especiaLLy chloride, sulphates and inorganic or organic phosphates of ammonium.

Other activators may be employed. The activators which normaLLy increase the herbicidal activity of glyphosate type compounds are also useful in the present invention when phenoxynitrobenzoic acid derivatives are empLoyed.

The quantity of activators employed in the compositions of the present invention may be between approximately 0.1% and approximately 500% of the quantity of the glyphosate type compound and preferably between approximately and approximately 350%. This percentage depends on the specific nature of the activators employed.

The doses for the compounds employed in the present invention may vary within wide limits, especially depending on the nature of the pLants to be eliminated and/or the degree of infestation of crops by weeds.

In general, the compounds according to the present invention usuaLLy contain approximately 0.05 to approximateLy 95% of one or more active ingredients according to the present invention, approximately 1 to approximately of one or more solid or liquid carriers and optionally, approximately 0.1 to approximateLy 50% of one or more I II 3 2 S0 P CH -N H CH 2 -Z (Ia) OR4 18 surface-active agents.

The compositions preferabLy contain 10% to 50% by weight of the combination of the two active substances of formulae and (VIII) and preferably 15% to As mentioned above, the active ingredients empLoyed in the present invention are generally combined with carriers and optionally with surface-active agents.

In the description of the invention, the term "carrier" denotes a natural or synthetic organic or inorganic ingredient with which the active ingredients are combined in order to facilitate its application to the plant, to seeds or to the soil. Therefore, this carrier is generally inert and it must be acceptable in agriculture, especially with respect to the plant treated. The carrier may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers and the like) or liquid (water, alcohols, especially butanol); esters, especially methylglycol acetate; ketones, especially cyclohexanone and isophorone; petroleum fractions; aromatic or paraffinic hydrocarbons, especially xylenes; chlorinated aliphatic hydrocarbons, especially trichloroethane, or chlorinated aromatic hydrocarbons, especially chlorobenzenes; water-soluble solvents such as dimethylformamide, dimethyl suLphoxide or N-methyLpyrrolidone; Liquefied gases and the like.

The tension-active (sic) agent may be an emulsifier, _2 dispersant or wetting agent of ionic or nonionic type, or a i are those in which R- and R which may be identical or /jR~ A different, represent Lower alkyL or aryl groups, and in 1 S/ which Z is a group COOR, R being a Lower alkyl or \7 7 19 alternatively, a mixture of these surface-active agents.

Examples include polyacrylic acid saLts, Lignosulphonic acid salts, phenolsulphonic or naphthaLenesulphonic acids, products of polycondensation of ethyLene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (especially aLkylphenols or aryLphenols), suLphosuccinic acid ester saLts, taurine derivatives (especially alkyl taurates), phosphoric esters of alcohols or of products of polycondensation of ehtylene oxide with phenols, esters of fatty acids with polyhydric alcohols, and derivatives having sulphate, sulphonate ard phosphate groups, of the 4 compounds above. The presence of at least one surfaceactive agent is generally valued.

For their appLication, the active ingredients empLoyed in the present invention are generally in the form of compositions. These compositions according to the present invention are themselves in different solid or Liquid forms. Forms of compositions of the present invention incLude water-soLuble powders (having an active ingredient content which may reach 80%) and water-soluble granules especially those obtained by extrusion, compacting, impregnation of a granular carrier, or by granulation starting with a powder (the active ingredient content in these granuLes being between approximateLy 0.5 and approximateLy 80% in the Latter cases) and aqueous solu- A RAI tions.

n aThe water-soLuble concentrates or soLutions r 0 etnytamine, methyliso-propylamine, methylhexylamine, methylnonylamine, methyLpentadecyLamine, methyloctadecyLamine, ethylbutylamine, ethylheptyLamine, ethyloctylamine, o LU 20 (especiaLly powders or granules) also most frequently contain approximately 5 to approximately 80% of active ingredients, whereas the emuLsions or solutions which are ready for appLication generally contain approximately 0.01 to approximately 20% of active ingredients. In addition to the soLvent, the solutions or concentrates may contain approximately 2 to approximately 50% of suitable additives such as stabilizers, surface-active agents, agents faciLitating penetration, corrosion inhibitors, colouring agents or adhesives.

Irrespective of the concentration required, emulsions which are particuLarLy suitable for application to plants may be prepared from these concentrates by diluting with water.

ALL these aqueous dispersions or solutions or mixtures may be applied to crop plants to be weeded, by any suitabLe means, for example by spraying, at rates which are generally of the order of approximately 100 to approximately 1,200 litres of spraying mixture per hectare.

The compositions according to the present invention are suitably applied to the vegetation and especiaLLy to the weeds to be destroyed, when the latter have a green foliage.

The non-Limiting examples below illustrate the i present invention and the way in which it can be applied "l Re A in practice.

Pal N' T c a r to t pre en t tV 1 witnout implied Limitation, those represented by the formuLa 21 i Example 1: Application of the herbicidal composition after the germination of different species of pLants (in gLasshouse) 7 x 7 x 8 cm pots are filled with Light sand for cropping, and a certain number of seeds, depending on the pLant species and the seed thickness, is pLanted.

The seeds are then covered with an approximately 3 mm thick Layer of soiL, and the seeds are allowed to germinate until they reach a convenient stage of growth.

The treatment stage for graminaceous type of pLaits is the "second-Leaf formation" stage. The treatment stage for dicotyledenous pLants is the "cotyledon opening and first true Leaf deveLopment" stage.

The pots are then treated by spraying a quantity corresponding to an application dose of 500 L/ha by volume, containing the active substances at their desired concentrations. The spraying mixture contains a container mixture, prepared by mixing: water, an aqueous solution containing 240 g/l of acifluorfen-sodium (the concentration in g/L as well as the doses in g/ha refer to the acid form of acifluorfen), and an aqueous solution containing 360 g/L of the isopropyLammonium or the N-phosphonomethylgLycine salt i (which is the acid form of gLyphosate; the concentration in g/L as well as the doses in g/ha refer to the acid f form), which also contains 15% of surfactant of the ,e i. i_ I 22 ethyLene oxide polycondensate derivative type.

Different active substance concentrations of the spraying Liquid are empLoyed, corresponding to the different doses of active substances applied.

The treated pots are then placed in tanks designed to receive irrigation water by sub-irrigation and they are maintained at ambient temperature for 24 days at a relative humidity of On the 13th and 29th days after treatment, the number of live plants in the pots treated with the spraying liquid containing the active substance to be tested are counted and the number of live plants in a control pot treated according to the same conditions, but with a spraying liquid which does not contain active substances is also counted. A percentage equal to 100% indicates that there is a total destruction of the plant species under consideration, and a percentage equal to 0% indicates that the number of live plants in the treated pot is identical to that in the control pot.

The plant species used in Example 1 are: Morning Glory (Ipomoea purpurea) and Potherb Purslane (Portulaca oleracea).

The tests carried out demonstrate the remarkably early herbicidal effect of the compositions according to the present invention in post-emergence treatments. (See Tables I and II at the end of the description).

23 Example 2:'FieLd experiments The fieLd was divided into 5 metre squared plots.

SeveraL species were sown in each plot, in rows 15 cm apart. These species incLuded the foLLowing monocoty- Ledonous plants: WiLd oat: Avena fatua (AVEFA) Cockspur grass: EchinochLoa crus-galli (ECHCG) Ryegrass: Lolium muLtiflorum (LOLMU) Panic grass: Panicum miLiaceum (PANMI) and the following dicotyledonous weeds: Pigweed: Amaranthus retroflexus (AMARE) Wild mustard: Sinapis arvensis (SINAR) When all the plants reached the 2-3 leaf stage, i.e. approximately 3 weeks after the sowing, treatments

J

were applied by preparing container mixtures of active ingredients at suitable concentrations and spraying them on the rows of plants at a volume of 500 1 per hectare in order to obtain adequate rates. An untreated plot was placed in contiguity with each treated plot for comparison and rating. The ratings were carried out at 1 ~different times after the treatment and are expressed as percentages of destruction for each species, in comparison with the same species in an untreated plot.

Herbicidal effect is observed 5 days after treatment. The same active ingredients and doses as the previous example were used. A remarkable early herbicidal R 7 effect was observed, as shown in Table III at the end of d the description.s K the description.

I i. -L ad ^l c~unrrslm~ll~~ 24 In this example the plants were leached by rain of water) 15 hours after treatment.

V

j. i in which: Zrepresents a chlorine atom or the group CF 3 25 TabLe r- Weed and da tes of t re at m en t gLyphos at e doses g /h a n o ac iflour fe n acifLuor-fen 10 g/ha Ipomoea PortuLaca T+13 T+29 P1T-13 T+29 Ipomoea 125 T+13 0 0 l/ fI/ T+L9 0 I /I 0 'ii II/ PortuLaca 125 T+13 0 /I 80 Iil T+29 10 Il III III Ipornoea 250 T+13 0 20 III IlI I/I T+29 0 /Il 20 I/I Il/ PortuLaca 250 T+13 0 IlI 98 //I T+29 20 III IIl IIl Among the Latter, acifluorfen-sodium is preferred.

According to the present invention, the new 26 TabLe II W-ied no acifLuorfen 20 g/ha and gLypho- acifLuor lpomoea PortuLaca dates sate of doses T+13 T+29 T+13 T+'29 treat- g/ha 0 0 20 m e nt Ipomoea 125 T+13 0 0 II /lII T+29 0 I/l 80 lIiII PortuLaca 125 T+13 0 II 90 l/ T+29 10 /1III /I Ipomoea 250 T+13 0 98 I/ /III T+29 0 lii 80 II!II Portutaca 250 T+13 0 III/I 100 /1 +29 I/I 100 7

V.

L

roots which are persistent in the soiL after the harvest.

Thus, it is possibLe to plant shortLy after the harvest

A

27 TabLe I Active Doses AVEFA ECHCG LOIMU PANMI AMARE SINAR ingredients acifLuorfen 50 9 7.5 6.5 7.5 25 22.5 s od i urn mixture of 200+5 27.5 35 37.5 37.5 60 the two active gLy- 400+5 70 67.5 62.5 67.5 70 phosate saLt formuLation s and acifLuorfen sodium .soL u tions. i

I

p l Llilili- l r~l -I L;IY-D;- ~li-i- i i;i~i-C^ -~i~il^i;~-Il-liii~il;?)-l-l-i _:LX 27A EXAMPLE 3 Comparative Tests In order to compare side by side the prior art and the present invention, additional tests were carried out on three weeds Centorea cyanus Echinochloa crusgalli Lolium multiflorum CENcy ECHcg LOLmu with the doses set out below 1 glyphosate isopropylammonium (G) acifluorfen sodium (A) 2 A 9 eu .9 B

B,

250 g/ha 11 g/ha 250 g/ha 22 250 g/ha 50 g/ha 250 g/ha 75 g/ha 3 G

A

4 G

A

0 6 *6 9 0 0

BB

The ratios and weight were respective for 1 22 for 1 11 for 1 for 1 3,3 is the ratio of the invention; in AU 26983/84.

The following results were obtained: are the ratios found 1 2 3 4 CENcy 100 81 65 ECHcg 64 60 50 LOLmu 42 35 18

Claims (10)

1. 2. The composition according to CLaim 1, wherein the ratio by weight phenoxybenzoic type herbicide:gLypho- sate type herbicide is between 1:15 and 1:50.
2. 3. The composition according to Claim 1, wherein the glyphosate type herbicide is of formula I OR' 0 P CHz NH CH 2 Z OR z in which Z is a cyano group or a group COOR; R is a hydrogen atom, or alternatively, is chosen from amongst Lower aLkyL, Lower aLkenyL or Lower aLkoxyaLkyl groups or an aryl group containing 6 to 10 carbon atoms and optionally carrying 1 to 3 substituents chosen inde- pendently from Lower alkyl, lower alkoxy, halo, trifluoro- methyl, nitro and cyano groups or alternatively is a com- patible cation which is capable of forming a saLt; R1 and R are identical or different, being hydrogen atoms S or being chosen from Lower alkyL, aryL, substituted aryL S/ or biphenyl groups, or alternatively, being compatible 1 cations which are capable of forming salts; 1 of one or more solid or Liquid carriers and optionaLLy, approximateLy 0.1 to approximately 50% of one or more ~yr I 'L I I- 29 or alternatively, the gLyphosate type herbicide is of formuLa la OR 3 0 P CHz N H, CH2 OR (la) in which: Z 2 is a compatible anion, capable of forming a salt; R and R are identical or different and repre- sent hydrogen atoms or Lower alkyl or aryL, Lower alkyl or substituted aryl or biphenyl groups; Z (sic) is a cyano group or a group COOR 5 and R is a hydrogen atom or alternatively is chosen from Lower alkyl, Lower alkenyl and Lower alkoxyalkyl groups; an aryl group containing 6 to 10 carbon atoms and optionally carrying 1 to 3 substituents independently chosen from Lower alkyl, lower aLkoxy, halo, trifluoro- methyl, nitro and cyano groups; and the phenoxybenzoic type herbicide is a com- pound of formula VIII R CO) -z9 I P -i- E j 2, i" pi r'i iri r (VIII)' in which: Z represents a chlorine atom or the group CF 3 The tension-active (sic) agent may be an emuLsifier, S dispersant or wetting agent of ionic or nonionic type, or 30 represents a chlorine or fluorine atom; 7 represents a hydrogen, chlorine or fluorine atom; 8 represents a chlorine atom or a nitro group; p has the value 0 or 1; R 13 and R 14 are identical or different and represent hydrogen atoms or methyl groups; and Z 9 represents a hydroxy, alkoxy or (lower)alkylsulphonamide, or alternatively a group OM in which M is an atom of an alkali metal or alkaline earth metal element.
3. 4. The composition according to Claim 3, wherein for compounds of formula (VIII), Z 5 is a chlorine atom, Z 6 is a group CF 3 Z 7 is a 8 hydrogen atom and Z is a nitro group. The composition according to Claim 4, wherein the compounds of formula (VIII) are chosen from amongst: fomesafene, benzofluorfen, 15 lactofene and preferably acifluorfen or one of its sodium or potassium salts and more particularly, acifluorfen-sodium.
4. 6. The composition according to any one of Claims 1 to 5, which S is in the form of a ready-for-use mixture. A method for the post-emergence treatment of weeds, which consists in applying to the latter an effective quantity of a glyphosate type herbicide and a quantity of a phenoxybenzoic type herbicide, wherein the dose of the glyphosate type herbicide is between 0.3 and 0.9 kg/ha and the dose of the phenoxybenzoic type herbicide is between 0.005 and 0.1 kg/ha, the ratio by weight of phenoxybenzoic type S. 25 herbicide:glyphosate type herbicide being between 1:12 and 1:80.
5. 8. The method according to Claim 7 wherein the dose of glyphosate-type herbicide is between 0.4 and 0.8 kg/ha.
6. 9. The method according to Claim 8 wherein the dose of glyphosate-type herbicide is between 0.5 and 0.7 kg/ha. 30 10. The method according to any one of Claims 7 to 9 wherein the dose of phenoxybenzoic type herbicide is between 0.02 and 0.08 kg/ha.
7. 11. The method according to any one of Claims 7 to 10 wherein the ratio is between 1:15 and 1:50.
8. 12. A weed treatment method which is destructive in its object, which makes it possible especially to gain control over the growth of the said weeds and optionally to destroy them totally or partially, the said weeds being at the end of their growth cycle and/or having a growth which STS 1334u s
9. 31- is slowed down by low temperatures and/or a low humidity, the said methods consisting in applying to the said weeds an effective quantity of a glyphosate type herbicide and a phenoxybenzoic type herbicide, wherein the dose of the glyphosate type herbicide is between 0.3 and 0.9 kg/ha and the dose of the phenoxybenzoic type herbicide is between 0.005 and 0.01 kg/ha, the ratio by weight phenoxybenzoic type herbicide:glyphosate type herbi'ide being between 1:12 and 1:80 13. The method according to Claim 12 wherein the dose of glyphosate type herbicide is between 0.4 and 0.8 kg/ha. 14. The method according to Claim 13 wherein the dose of glyphosate type herbicide is between 0.5 and 0.7 kg/ha. The method according to any one of Claims 12 to 14 wherein the dose of phenoxy- benzoic type herbicide is between 0.02 and 0.08 kg/ha. 16. The method according to any one of Claims 12 to 15 wherein the 15 ratio is between 1:15 and 1:50. 17. A method for preventing a glyphosate type herbicide from being Swashed out by possible rainfalls after it is applied as a post-weed- Semergence treatment, which consists in applying to the said weeds an s effective quantity of phenoxybenzoic type herbicide, wherein the dose of the glyphosate type herbicide is between 0.3 and 0.9 kg/ha, and the dose of the phenoxybenozic type herbicide is between 0.005 and 0.1 kg/ha and the ratio by weight of phenoxybenzoic type herbicide:glyphosate type Sherbicide is between 1:12 and 1:80. 18. The method according to Claim 17 wherein the dose of S 25 glyphosate type herbicide is between 0.4 and 0.8 kg/ha. "os 19. The method according to Claim 18 wherein the dose of glyphosate type herbicide is between 0.5 and 0.7 kg/ha. 20. The method according to any one of Claims 17 to 19 wherein the dose of phenoxybenzoic type herbicide is between 0.02 and 0.08 kg/ha. 30 21. The method according to any one of Claims 17 to 20 wherein the ratio is between 1:15 and 1:50. 22. The composition according to any one of Claims 1 to 6, which is intended to be diluted in water with a view to applying it to plants, which contains 10% to 50% by weight of the combination of the two active substances of formula and (VIII). 23. The composition according to Claim 22 wherein the ratio by weight is 15 to 1334u -Milo I low I
10. 32- 24. A herbicidal composition containing at least one glyphosate type herbicide and at least one phenoxybenzoi c type herbicide .Substantially as hereinbefore described with reference -to Example 1 or Example 2. 25. The method for the post-emergence treatment of weeds substantially as hereinbefore described with reference -to Example 1 or Example 2. DATED this TWENTY-SEVENTH day of JUNE 1991 Rhone-Poulenc Agrochimie Patent Attorneys for the Applicant *SPRUSON FERGUSON M S 33 (which is the acid form of gLyphosate; the concentration in g/L as weLL as the doses in g/ha refer to the acid i form), which also contains 15% of surfactant of the T ON Company caLLed: RHONE-FO t NC AGROCHIMIE ABSTRACT "Herbicidal compositions based on a glyphosate type herbi- cide and a phenoxybenzoic type herbicide and method for the treatment of undesirable plants using these compositions" Herbicidal composition containing at least one glyphosate type herbicide and at Least one phenoxybenzoic type herbicide, preferabLy acifLuorfen-sodium, the ratio by weight phenoxybenzoic type herbicide:glyphosate type herbicide ranging between 1:12 and 1:80, preferabLy be- tween 1:15 and 1:50. This composition is especiaLLy resistant to being washed out during rainfaLL events occurring shortLy after application. -L t