DD248498A5 - HERBIC MEDICINE AND ITS USE - Google Patents

Abstract

A herbicidal composition containing as active ingredient bromoxynil and / or ioxynil and diflufenican in addition to a conventional carrier or dismutating agent and optionally further additives and herbicides is particularly suitable for controlling a wide range of grassy and broadleaf weeds in cereal crops. The active ingredients can also be applied successively, at intervals of a few minutes.

Description

For this 1 page drawing

Field of application of the invention

The invention relates to a novel herbicidal composition which is useful as a pre- or post-emergence herbicide, especially in cereal crops.

Characteristic of the known technical solutions:

GB-A-2 087 887 discloses N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide of the formula I

described as pre-emergence and / or post-emergence herbicide, as well as its use in agriculture.

It is also known that bromoynil (3,5-dibromo-4-hydroxybenzonitrile) and loxynil (4-hydroxy-3,5-diiodobenzonitrile) are widely used for post-emergence weed control for broadleaf (dicotyledonous) plants in cereal crops.

When used to control weeds at the "seedling" stage to eliminate early competition, they are extremely effective, however, because of their lack of residual activity in the soil, they do not affect the weeds, which only build up after use or delaying the spraying until the majority of the weeds have accumulated, but at which time the oldest weeds have already exerted considerable competition on the crops, and certain broad-leaved weed species such as Stellaria media, Galium aparine, Viola tricolor, Viola arvensis and Veronica hederifolia with the Toxynil and especially with Bromoxynil difficult or little fight.

Bromoxynil and loxynil also do not display useful activity against annual grass weeds.

Object of the invention

The aim of the invention is a herbicidal composition having a broader spectrum of activity than the known HBN herbicides bromoxynil

Explanation of the essence of the invention

It has now been found that the use of the compound N - (, 24-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide hereinafter referred to simplify diflufenican - in combination with the HBN herbicides bromoxynil and / or loxynil

a) contributes to residual soil activity, allowing for early application and elimination of weeds competition without repeated applications,

(b) the range of weeds that can be fought extended to weeds such as Stellaria media, Galium aparine and Viola arvensis, and

(c) the extermination of annual grasses, such as Alopecurus myosuroides, Apera spicaventi, Poa annua, Poa trivialis, Echinochloa crus-galli and Digitaria sanguinalis, when applied before emergence in crop plants.

"HBN herbicides" are bromoxynil and loxynil in the form of their underlying phenols (acid equivalent), agriculturally acceptable salts or esters thereof, preferably metal or amine salts or esters with a C ₂ to C ₁₀ alkanoic acid or mixtures thereof, preferably 3 : 1 to 1 ² 3 w / w of mixtures, calculated as acid equivalents.

The said combined use therefore represents an important technological advantage. Surprisingly, it has additionally been found that the combined herbicidal activity of diflufenican and HBN herbicides is much greater than expected for many weed species when applied after emergence, for example as post-emergence sprays , d. H. The herbicidal activity of diflufenican and HBN herbicide shows an unexpected and notable degree of synergism with numerous weed species, for example against Setaria viridis, as reviewed by PML Tammes, Netherlands Journal of Plan Pathology, 70 (1964), pp. 73-80 entitled "Isoboles, a graphic representation of synergism in pesticides", as well as Veronica hederifolia, Anthemis cotula, Vicia sativa, Epilobium paniculatum, Lamium amplexicaule, Montia linearis and Sisymbrium altissimum, as cited by Limpel, L E., PH Schuldt and D. Lamont, 1962, Proc. NEWCC 16: 48-53 defined using the formula

in E the expected percentage inhibition of growth by a mixture of two herbicides at defined doses, X the percentage growth inhibition by the herbicide A at a defined dose and

Y is the percentage growth inhibition by the herbicide B at q of a defined dose.

If the observed effect is greater than expected, the combination is synergistic.

The remarkable synergistic effect of the post-emergence mixture results in improved reliability in controlling numerous weed species that occur in cereal crops and therefore allows for a reduction in the amount of active ingredient applied.

In accordance with the present invention, weeds are controlled in pre-emergence or post-emergence crops by combining (a) bromoxynil, ie 3,5-dibromo-4-hydroxybenzonitrile, or loxynil, ie 4-hydroxy-3,5-diiodobenzonitrile, an agriculturally acceptable (r ) Salt or ester thereof, preferably a metal or amine salt, or an ester with a C ₂ to C ₁₀ alkanoic acid or a mixture thereof, preferably a 3: 1 to 1: 3 w / w. Mixture, calculated as acid equivalents and (b) Diflufenican in application rates of 100 to 500 g of acid equivalent (S.A.) / ha (a) and from 25 to 250 g / ha (b) in proportions of 20: 1 to 2: 5 , preferably from 8: 1 to 1: 1 w / w. (a) to (b) be applied to control a wide range of weed species in cereal crops, for example in wheat, barley, rice and maize crops, preferably shortly after emergence of the weeds after emergence of the crops without appreciable permanent Damage to crops. The combined application causes both leaf activity and residual activity.

"Pre-emergence treatment" refers to application to the soil in which the weed seeds or seedlings are present before appearing on the soil surface. "Postemergence treatment" refers to application to the overlying or exposed portions of the soil Weeds designated. "Leaf Activity" means the herbicidal activity produced by application to the above-ground or exposed portions of the weeds. "Residual Activity" refers to the herbicidal activity that is brought about by application to the soil in which the weed seeds or weed seeds Seedlings are placed over the soil surface prior to emergence, thereby eliminating the seedlings present at the time of application or germinating from seeds present in the soil after application.

In accordance with the invention, the use of one or more of the above-defined esters of the HBN herbicide is preferred. Above all, the esters with Cu to Cg alkanoic acids are preferred, in particular the octanoates or heptanoates or mixtures thereof. Very particular preference is given to the use of bromoxyniloctanoate and / or heptanoate.

Weeds that can be controlled by the method include: among the broad-leaved weeds Aethusa cynapium, Abutilon theophrasti, Amaranthus retroflexus, Amsinckia intermedia, Anagallis arvensis, Anthemis arvensis, Anthemis cotula, Atriplex patula, Bensens pilosa, Brassica nigra, Capsella bursa -pastoris, Chenopodium album, Chrysanthemum segetum, Cirsium arvense, Datura stramonium, Desmodium tortuosum, Emex australis, Epilobium paniculatum, Euphorbia helioscopia, Fumaria officinalis, Galeopsis tetrahit, Galium aparine, Geranium dissectum, Ipomea purpurea, Lamium amplexicaule, Lamium purpurum, Lapsana communis , Matricaria inodora, Monochoria vaginalis, Montia linearis, Papaver rhoeas, Physalis longifolia ,.

Plantago lanceolata, Polygonum spp. (eg Polygonum aviculare, Polygonum convolvulus and Polygonum persicaria), Portulaca oleracea, Raphanus raphanistrum, Rotala indica, Rumex obtusifolius, Saponaria vaccaria, Scandix pectenveneris, Senecio vulgaris, Sesbania florida, Sida spinosa, Silene alba, Sinapis arvensis, Sisymbrium altissimum Solanum nigrum, Sonchus arvensis, Spergula arvensis, Stellaria media, Thlaspi arvense, Tribulus terrestria, Urtica urens, Veronica hederifolia, Veronica persica, Vicia sativa, Viola arvensis and Xanthium strumarium; among the weeds Alopecurus myosuroides, Apera spicaventi, Agrostis stolonifera, Poa annua, Poa trivalis, Digitaria sanquinalis, Echinochloa crus-galli, Eleusine indica, Setaria viridis, and under the sedges or creepers Cyperus iria and Eleocharis acicularis.

The duration-of-effect patterns of the HBN herbicide and diflufenican also allow for the time-delayed application of separate formulations.

In accordance with common practice, a tank mix may be prepared prior to use by combining separate formulations of the individual herbicidal components.

The invention is explained in more detail by the following experiments:

Trial 1

The following greenhouse experiment demonstrates the synergistic activity of the combined use of bromoxynil and diflufenican in combating the growth of Setaria viridis.

Greenhouse trial showing the biological synergism between Bromoxynil and Diflufenican.

An experiment with 25 individual treatments was conducted to investigate the interaction of bromoxynil and diflufenican in a wide dose range; d. H. Bromoxynil-triethylamine (Example 1 below) at a dose of 0.125, 250, 500 and 1000 g of S.a. (Acid equivalent) / ha plus Diflufenican (Example 2 below) in a dose of 0.125, 250, 500 and 1000 g of active ingredient / ha, as indicated in the following list were in an injection volume of 260 l / ha for every three pots with 9 cm in diameter, containing in each case 5 seedlings of Setaria viridis in the 2-leaf stage in John Innes No. 1 planting soil. After spraying, the pots were irrigated in an arbitrary block arrangement in the greenhouse in the necessary manner and the percentage phytotoxicity, compared with non-treated plants, evaluated after three weeks (0 = no effect, 100 = complete eradication).

Bromoxynil-triethylamine g S.A. / ha

treatment (1) (6) + (11) + (16) + (21) 125 250 500 0 125 1 000 250 1 000 500 1 000 1 000 (23) (24) (25) (2) (7) (12) (17) (22) 1 000 1 000 1 000 125 250 500 1 000 + + + 125 + + + + 1 000 125 125 125 (3) (8th) (13) (18) 125 250 500 250 + + + Diflufenican g / ha 250 250 250 (4) (9) (14) (19) 125 250 500 500 + + + 500 500 500 (5) (10) (15) (20) 125 250 500 1 000

The following results were obtained:

Bromoxynil triethylamine

0 0 0 0 0 % Phytotoxicity 30 40 45 50 70 Diflufenicarr 38 40 50 60 80 45 60 60 80 90 60 70 80 100 100

From these results, the ED 50 values, i. H. the effective dose giving 50% phytotoxicity is plotted in g / ha for diflufenican alone and with increasing levels of bromoxynil-triethylamine. Bromoxynil-triethylamine had no activity by itself. The following EDaj values were obtained:

125 g / ha ED ₅₀ g / ha Diflufenican (Dif.) 250 g / ha 625 Dif. + Bromoxynil 500 g / ha 325 Dif. + Bromoxynil 1 000 g / ha 225 Dif. + Bromoxynil 150 Dif. + Bromoxynil 75

The results were then used to record an isobole having a "one-sided effect" according to P.M.L. Tammes, Netherlands Journal of Plant Pathology 70, 1964, pp. 73-80 "Isoboles, a graphic representation of synergism in pesticides". The obtained isobole was clearly a type II curve (Tammes, p. 74, Fig. 1) characteristic of synergism (following Fig. (1)).

Trial 2

A winter wheat tree in the 3- to 5-leaf stage that had become usurped with Veronica hederifolia at the 10- to 16-leaf stage was treated with bromoxyniloctanoate (formulation Example 4) at a dose of 0.28 kg S.A./ha and diflufenican (Formulation Example 2) in a dosage of 0.14 kg / ha and a tank mix of the two sprayed in a dosage of 20 gpa (g / 4047 m ² ). In each case four 2.44 m χ 7.62 m (8 'χ 25') randomly arranged plots were treated. Forty-seven days after splashing, the damage of the plants and the orozentual vertebrate of the weeds were evaluated. The results are consequential

treatment

% Damage% Extermination of the grain of Veronica hederifolia

Bromoxynil-octanoate 0 15 0.28 g S.A. / ha (0.25 Ib / ac) diflufenican 0 60 0.144 g S.A./ha (0.125 Ib / ac) Brom.oct. + Dif. 0.28+ 0.144 g S.A./ha 0 94 (0.25 + 0.125 Ib / ac)

XY

Using the Limpel formula: ^ = X + Y = T ^ r

The observed effect on Veronica hederifolia was much stronger than expected, and the combination proved to be clearly synergistic.

The crop compatibility was excellent.

Trial 3

A winter wheat field in the 2- to 3-leaf stage, weeds with Anthemis cotula (2- to 6-leaf stage), Vicia sativa (2- to 4-leaf stage) and Epilobium paniculatum (2- to 6-leaf stage) was used in the same manner as in Trial 2 treated and assessed the crop damage and weed kill at 47 days. The results (averages of four trials each) are as follows:

% Damage% Extermination of

of cereal Anthemis vicia epilobium

Bromoxynil-octanoate 0 15 0 3 0.28 g / ha (0.25 lb / ac) diflufenican 0 43 80 75 0.144 g / ha (0.125 Ib / ac) Brom.oct. + Dif. 0.28 + 0.144 g / ha 0 98 99 100 C0.25 +0.125 Ib / ac)

The predicted extermination of Anthemis, Vicia and Epilobium calculated using the Limpel formula was 52, 80 and 76 (%); this clearly shows that the combination was synergistic. The crop compatibility was excellent.

Trial 4

Winter wheat at the 4- to 6-leaf stage, which was ushered in with Lamium aplexicaule (4- to 10-leaf stage), Montia linearis (6 to 10-leaf stage) and Sisymbrium altissimum (4 to 8-leaf stage), was treated in the same way as treated in experiment 2; damage to crops and weed eradication was evaluated 41 days after spraying. The results (averages of four trials each) are as follows:

% Damage% Extermination of

of the cereal Lamium Montia sisymbrium

Bromoxynil-octanoate 0 15 13 63 0.28 g / ha (0.25 lb / ac) diflufenican 0 23 18 18 0.144 g / ha (0.125 Ib / ac) Brom.oct. + Dif. 0.28 + 0.125 g / ha 0 94 97 99 (0.25 + 0.125 Ib / ac)

The expected values for Lamium, Montia and Sisymbrium are 34, 29 and 70; Thus, the mixture proved to be clearly synergistic. The crop compatibility was excellent

Trial 5

The efficacy of these synergistic mixtures for weed control in spring wheat and barley was demonstrated in field trials on small plots, comparing a combination of bromoxynil ester and diflufenican with bromoxynil ester and with diflufenican, each alone. Diflufenican (Example 2 below) in an application rate of 150 g / ha, Bromoxynil-octanoate (commercial formulation) at a rate of 210 g S.A. / ha and a tank mix of the two at an application rate of 102.9 l / ha were on two wheat fields and a barley field, each in the 2- to 5-leaf stage, applied. Each experiment was repeated three times to 17.5 to 25 m ² large parcels carried out using a motorized sprayer. The effect against weeds and the safety and / or compatibility for the crops was assessed visually two weeks after spreading according to the following scale:

rating scale

(ECW Western Canada) 1983

Weed killing _o

Useful plant tolerance

9 complete eradication 9 complete tolerance

8 excellent eradication 8 possible effect

- commercially acceptable -

7 good eradication 7 easy effect

6 little eradication 6 distinct effect

5 bad eradication 5 strong effect

4 moderate damage 4 strong effect

3 distinct effect 3 strong effect

2 weak effect 2 strong effect

1 possible effect 1 strong effect

O no effect O complete kill

The results are summarized in the following Table I:

Table I

Medium weed eradication and crop tolerance ECW scale

treatment S. V. T. a. Ch. A. F. t. A. r. wheat barley diflufenican 150 g / ha 4.8 5 1 0 6 9 9 diflufenican 150 g / ha bromoxynil octanoate 210 g S././ha 8.8 9 9 9 9 9 9 bromoxynil octanoate 210 g S././ha 2.1 7.8 9 8th 7.3 9 9 Occur number 2 1 2 1 1 2 1

P. V. = Setaria viridis

T. a. = Thlaspi arvense

Ch. A. = Chenopodium album

F. t. = Fagopyrum tartaricum

A. r. = Amaranthus retrofluxus

Trial 6

The efficacy of these blends to control Galium aparine, Veronica hederifolia and Viola tricolor has been demonstrated in the following field trials in which a bromoxynil ester / diflufenican tank mix with bromoxynil ester alone was compared.

Bromoxyniloctanoate (commercial product) at a rate of 250 g of S.I./ha and a tank mixture of bromoxyniloctanoate plus 150 g / ha of diflufenican (Example 2 below) was applied to small plots in a volume of 330 to 500 l / ha (15 to 30 m ² ) of two winter wheat and two winter barley fields using a backpack sprayer applied. The weed and tolerability for the crop were 20 to 30 days after spraying by percent ^D hytoxizität evaluated in comparison with untreated plots. The results are given in the following Table II:

Table I

Mean phytotoxicity, <

treatment G a V. h. V t Winter wheat barley 1 3 2 Bromoxyniloctanoate 250 g S.A./ha Bromoxynil-oct. 250 g S.A. / ha diflufenican 150 g / ha incidence 70 95 1 7 82 2 47 98 2 1 1 2 G. a. = Galium aparine V. h. = Veronica hederifolia V. t. = Viola tricolor

Trial 7

The efficacy of the blends was demonstrated in the following field trials in which a tank mix containing bromoxynil potassium salt (Example 3 below) plus diflufenican (Example 2 below) was compared to diflufenican alone.

One acreage of winter wheat and three winter barley cultivars were grown at a dose of 125 g / ha with diflufenican and with a tank mixture of diflufenican 125 g / ha plus bromoxynil K salt 300 g S.A./ha a quantity of 220 to 235 l spraying liquid per ha, treated using a motorized sprayer for small plots.

In each area three plots a 30 m ^{2 were} spray-treated for each trial.

Weed eradication was assessed in late spring, after early spring and winter applications, by counting the number of weeds in 2 χ 0.5 m ² squares per plot and percentage calculation compared to untreated plots. The safety of the crops was determined visually according to a phytotoxicity rating scale of 0 to 100%, where 0% means complete destruction.

The results are summarized in the following Table III.

Table III

Diflufenican 125 g / ha

Bromoxynil-K salt

% Weed kill

Crop phytotoxicity

treatment P.A. S. m. V. P. V. a. Approximately C. b. p. Lh. M. i. P. r. Winter wheat barley Diflufenican 125 g / ha 69 90 95 90 100 100 99 44 66 0 0.83

300 g S././ha 86 96 99 98 100 100 100 95 98 0 1.38 Occur 2 3 3 2 1 1 1 1 2 1 3

P. a. = Poa annua S. m. = Stellaria media V. P- = Veronica persica V; 3, Viola arvensis C. a. = Cerastium arvensis C. b. ? = Capsella bursa pastoris P- L. H. = Legousia hybrida M , i. = Matricaria inodora P. r. = Papaver rhoeas

These experiments clearly demonstrate the broad spectrum of weed control including Setaria viridis, Galium aparine, Veronica and Viola, which can be achieved with the synergistic mixtures.

According to a further feature of the invention, the herbicidal agents contain (a) bromoxynil, d. H.

3,5-dibromo-4-hydroxybenzonitrile, or loxynii, ie 4-hydroxy-3,5-diiodobenzonitrile, an agriculturally acceptable salt or ester thereof, preferably a metal or amine salt, or an ester having a C ₂ to C ₁₀ alkanoic acid or a mixture thereof, preferably a 3: 1 to 1: 3 Gew./Gew. A mixture, calculated as acid equivalents and (b) Diflufenican in a ratio by weight of from 20: 1 to 2: 5, preferably from 8: 1 to 1: 1, combined with - and preferably homogeneously distributed in - one or more for herbicides conventional diluents or carriers and / or surfactant (s), ie diluents or carriers, or surfactants of the type commonly used for herbicidal agents and which are compatible with the HBN herbicide and diflufenican. "Homogeneously distributed" also refers to those agents in which the HBN herbicide and diflufenican are dissolved in the other components. "Herbicidal agent" in the broadest sense means not only ready-to-use agents but also concentrates which must be diluted before use. Preferably, the agents contain from 0.05% to 90% by weight of HBN herbicide and diflufenican.

The herbicidal compositions may contain both a diluent or a carrier and a surfactant, for example a wetting agent, dispersant or emulsifier. The surfactants which may be present in the herbicidal agents may be ionic or nonionic, for example sulforicinoleates, quaternary ammonium derivatives, condensation products of ethylene oxide and nonyl or octylphenols or carboxylic esters of anhydrosorbites which have been solubilized by etherification of the free hydroxy groups with ethylene oxide , Alkali and alkaline earth salts of sulfuric acid esters and sulfonic acids, such as dinonyl and dioctyl sodium sulfono-succinates and alkali and alkaline earth metal salts of high molecular weight sulfonic acid derivatives, such as sodium and calcium lignosulfonates. Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesia, diatomaceous earth, tricalcium phosphate, cork powder, activated carbon and clays such as kaolin and bentonite. The solid agents, which may be in the form of dusts, granules or wettable powders, are preferably prepared by grinding the HBN herbicide and diflufenican with solid diluents or by impregnating the solid diluents or carriers with solutions of the HBN herbicide and diflufenicans in volatile solvents, evaporation of the solvents and optionally grinding the products thus obtained to a powder. Granules can be prepared by absorbing the HBN herbicide and diflufenican dissolved in volatile solvents, from the solid diluents or carriers in granular form and evaporating the solvents or by granulating powdery agents obtained as described above. Solid herbicidal agents, especially wettable powders or wettable powders, may contain wetting or dispersing agents, for example of the types described above, which, when solid, may also serve as diluents or carriers.

Liquid compositions of the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may contain a surfactant. Suitable liquid diluents for the preparation of these liquid agents are water, acetophenone, cyclohexanone, N-methylpyrrolidone, isophorone, toluene, xylene and oils of mineral, animal or vegetable origin and mixtures thereof. Surfactants, which may be present in the liquid agents, may be ionic or nonionic, for example of the types described above, and, when liquid, may also serve as diluents or carriers.

Wettable powders and liquid concentrates may be diluted with water or other suitable diluents, such as mineral oils or vegetable oils, especially if they are liquid concentrates, where the diluent or carrier is an oil, ready to use to obtain. If desired, the liquid agents of the HBN herbicide and diflufenicans may be used in the form of self-emulsifying concentrates containing the active ingredients dissolved in the emulsifying agents or in solvents containing emulsifying agents or emulsifying agents compatible with the active substances; simply adding water to such concentration gives the ready-to-use agents. Liquid concentrates in which the diluent or carrier is an oil can be applied without further dilution by electrostatic spraying.

Herbicidal agents according to the invention may also contain, if desired, conventional additives such as adhesives, protective colloids, thickeners, penetrants, stabilizers, scavengers, anticaking agents, dyes and corrosion inhibitors. These additives can also serve as carriers or diluents.

Preferred herbicidal agents according to the invention are aqueous suspension concentrates containing 10 to 70% w / v. HBN herbicide and diflufenican, 2 to 10% w / v. Surfactant, 0.1 to 5% w / v. Thickener and 15 to 87.9 vol .-% water; wettable powders or spray powders containing 10 to 90% w / w HBN herbicide and diflufenican, 2 to 10% w / w. surfactant and 10 to 88% w / w. contain solid diluent or carrier; liquid water-soluble concentrates containing 10 to 30% w / v. HBN herbicide and diflufenican, 5 to 25% w / v. surfactant and 45 to 85% by volume of water-miscible solvent, for example dimethylformamide or N-methylpyrrolidone; liquid emulsifiable suspension concentrates containing 10 to 70% w / v. HBN herbicide and diflufenican, 5 to 15% w / v. Surfactant, 0.1 to 5% w / v. Thickener and 10 to 84.9% by weight of organic solvent; Granules containing 2 to 10% w / w. HBN herbicide and diflufenican, 0.5 to 2% w / w. surfactant and 88 to 97.5% w / w. granules and e.nulgierbare concentrates containing 0.05 to 90% w / v, preferably 1 to 60% w / v. HBN herbicide and diflufenican, 0.01 to 10% w / v. and preferably 1 to 10% w / v. surfactant and 9.99 to 99.94%, preferably 39 to 98.99% by volume of organic solvent. Herbicidal agents according to the invention may also contain the HBN herbicide and diflufenican in combination with, and preferably homogeneously dispersed in, one or more further pesticidal compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surfactants and usual additives as described above. Examples of other pesticidal compounds which may be included in, or used with, the herbicidal compositions of the present invention, for example to broaden the spectrum of weed species being challenged, include alachlor = a-chloro-2,6 diethyl-N (methoxymethyl) acetanilide, asulam = methyl (4-aminobenzenesulfonyl) carbamate, alloxydim Na = Na salt of

2- (1-Allyloxyaminobutylidine) -5,5-dimethyl-4-methoxycarbonylcyclohexyn-1,3-dione, atrazine = (2-chloro-4-ethylamino-6-isopropylamine) -1,3,5-triazine, Barban logo CNRS logo INIST 4-Chlorobut-2-ynyl-N- (3-chlorophenyl) carbamate, benzoylprop-ethyl = ethyl-N-benzoyl-N- (3,4-dichlorophenyl) -2-aminopropionate, especially bromoxynil = S-dibromo ^ -hydroxy-benzonitrile, butachlor = N-fButoxymethylJ-a-chloro ^^ - diethylacetanilide, butylate = S-ethyl-N, N-diisobutyl (thiocarbamate), carbetamide logo CNRS logo INIST

DN-ethyl-2- (phenylcarbamoyloxy) propionamide, chlorophenpropmethyl = methyl-2-chloro-2- (4-chlorophenyl) propionate, chloropropham = isopropyl-N-fS-chlorophenylcarbamate, cyanazine = 2-chloro-4- (1 -cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine, cycloate = N'-cyclohexyl-N-ethyl-S-ethyl-thiocarbamate), 2,4-D = 2,4-dichlorophenoxyacetic acid, dalapone logo CNRS logo INIST 2,2-Dichloropropionic acid, 2,4-DB = 4- (2,4-dichlorophenoxy) butyrate, Desmedipham = S-fethoxycarbonylamino-phenyl-N-phenyl-carbamate, dialate = S, S-dichloroallyl-N, N-diisopropylthiocarbamate), Dicamba logo CNRS logo INIST SB-dichloro-methoxybenzoic acid, dichlorprop = (±) -2- (2,4-dichlorophenoxy) propionic acid, diclofop = (RS) -2-4- (2,4-dichlorophenoxy) phenoxy-propionic acid, difenzoquat = 1 ^ - Dimethyl-S-diphenylpyrazolium salts, dimefuron = 4- (2-chloro-4- (3,3-dimethylureido) phenyl) -2-t-butyl-1,3,4-oxadiozolin-5-one, dinitramine logo CNRS logo INIST N ', N ¹ -diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine, EPTC = S-ethyl-N, N-dipropyl (thiocarbamate), ethofumesate = 2-ethoxy-2,3-dihydro-3 , 3-dime ethyl benzofuran-5-yl methylsulfonate, flampropisopropyl = isopropyl (±) -2- (N-benzoyl-3-chloro-4-fluoroaniline) propionate, flamprop-methyl logo CNRS logo INIST

Methyl (+) -2- (N-benzoyl-3-chloro-4-fluoroaniline) propionate, fluometuron = N '- (3-trifluoromethylphenyl) -N, N-dimethylurea, isoproturon = N' - (4-isopropylphenyl ) -N, N-dimethylurea, Linuron = N'-fSADichlorophenyl J-N-methoxy-N-methylurea, MCPA = 4-chloro-2-methylphenoxyacetic acid, MCPB = 4- (4-chloro-2-methylphenoxy) butyric acid, Mecoprop = (±) -2- (4-chloro-2-methylphenoxy) propionic acid, metamitron = 4-amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one, Methabenzothiazuron = N- (benzothiazol-2-yl-N, N'-dimethylurea, metribuzin = 4-amino-6-t-butyl-3- (methylthio) 1,2,4-triazine-5 (4H) -one, Molinate = S-ethyl N, N-hexamethylene-thiocarbamate), oxadiazone logo CNRS logo INIST

3- (2,4-dichloro-5-isopropoxyphenyl) -5-t-butyl-1,3,4-oxadiazolin-2-one, paraquat = 1,1-dimethyl-4,4'-bipyridylium salts, pebulate = S-propyl-N-butyl-N-ethyl-thiocarbamate), phenmedipham = S-f-methoxy-carbonyl-amino-phenyl-N-f S -methylphenyl-carbamate, prometry = 4,6-bis (isopropylamino) -2-methylthio-1,3,5-triazine , Propachlor = a-chloro-N-isopropyl-acetanilide, propanil = N- (3,4-dichlorophenyl) -propionamide, propam = isopropyl = N-phenylcarbamate, pyrazon = 5-amino-4-chloro-2-phenylpyridazine-3 (2H) -one, simazine = 2-chloro-4,6-bisethylamino-1,3,5-triazine, TCA = trichloroacetic acid, thiobencarb = S- (4-chlorobenzyl) -N, N-diethylthiolcarbamate, triallate = S ^ ^ .S-trichloroallyl-N, N-di-isopropylthiocarbamate) and trifluralin = 2,6-dinitro-N, N-dipropyl-4-trifluoromethylaniline; Insecticides such as carbaryl = naphth-1-yl-N-methylcarbamate; synthetic pyrethroids, such as permethrin and cypermethrin; and fungicides such as 2,6-dimethyl-4-tridecylmorpholine, methyl N- (1-butylcarbamoyl-benzimidazole) -yl-carbamate, 1-bis-bis-methoxy-carbonyl-thioureido-benzene, isopropyl-1-carbamoyl- S- ^ ö-dichlorophenylhydantoin and 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one. Other biologically active substances, which can be included in or used in conjunction with the herbicidal compositions of the invention are plant growth regulators such as succinic acid, (2-chloroethyl) trimethyl ammonium chloride and 2-chloroethane phosphonic acid, or fertilizers which For example, nitrogen, potassium and phosphorus, as well as trace elements that are essential for the good growth of plants, such as iron, magnesium, zinc, manganese, cobalt and copper.

Pesticidal compounds and other biologically active substances which may be incorporated in or used in conjunction with the herbicidal compositions of the present invention, for example those mentioned above and which are acids, may, if desired, be in the form of common derivatives, for example alkali salts and amine salts and esters. Preferred herbicidal compositions according to the invention which comprise the HBN herbicide and diflufenican combined with a further herbicide are those in which the further herbicide contain are those in which the further herbicide diclofop, MCPA or mecoprop or an agriculturally acceptable ( r) salt or ester thereof.

According to a further feature of the invention is additionally diclofop, MCPA or mecoprop or an agriculturally acceptable salt or ester thereof, preferably at application rates of 500 to 1500 g Sa / ha, or 100 to 1500 g S.ä. / ha or 1000 to 2500 g of S./ha./ha are applied, the corresponding preferred amounts being 570 to 1140 g S.I./ha., Or 150 to 1000 g S.A./ha. And 1000 to 2000 g S.A. / ha for weed control in cereal crops, preferably small grain crops such as wheat and barley.

The compositions of the present invention may be provided as an article of manufacture containing the HBN herbicide and diflufenican and optionally other pesticidal compounds as described above or, as preferred, as a herbicidal agent as described above, and preferably as a herbicide Concentrate which must be diluted before use, comprising the HBN herbicide and diflufenican within a container for the aforementioned HBN herbicide and diflufenican and said herbicidal agent, as well as instructions associated with and indicating the said container in which The intention is to use the said HBN herbicide and diflufenican or herbicidal weed control agent contained therein. The containers are generally conventional containers for the storage of chemical substances which are solid at normal ambient temperatures and of herbicidal agents, in particular in the form of concentrates, for example cans and canisters made of metal, which may be internally lacquered, or which consist of plastic , Glass and plastic bottles, and when the contents of the container is a solid, for example, a granular herbicidal agent, boxes, for example of cardboard, plastics and metal or bags. The containers are generally spacious enough to accommodate amounts of active ingredients or herbicidal compositions sufficient to treat at least 4,047 m ² Land for the purpose of weed control, but should not exceed the appropriate methods for the normal handling size. The instructions are physically attached to the container, for example printed directly on it, or on a sticker, or a tag. The instructions usually indicate that the contents of the container, optionally after dilution, should be used to control the growth of the weeds, at rates of from 100 to 500 g of Sa HBN herbicide and from 25 to 250 g diflufenican per hectolitre in the above described manner and for the purposes described above.

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embodiments

Examples 1

A water miscible agent containing bromoxynil triethylamine salt was prepared from:

bromoxynil ad 34% Gew./Vol. triethylamine 15% Gew./Vol. Soprophor BSU (Tristyrylphenol / Ethylene oxide condensate containing 18 moles of ethylene oxide) 1.5% Gew./Vol. diethylene glycol 25% Gew./Vol. water 100% Gew./Vol.

A portion of the water containing diethylene glycol, bromoxynil and triethylamine (15% w / v triethylamine represents a 2.6% by weight excess of triethylamine over the stoichiometric amount necessary to form the bromooxynil triethylamine salt) was heated and stirred mixed together. Then the tristyrylphenol / ethylene oxide condensation product was added and the volume made up to 100% with water.

Example 2

An aqueous suspension concentrate was prepared from:

Diflufenican 50% w / v

Ethylan BCP (a nonylphenol)

Ethylene oxide condensate

containing 9 moles of ethylene oxide each

mol of phenol) 0.5% w / v.

Soprophor FL (triethanolamine salt

of an oxyethylated polyarylphenol

phosphate) 1.0% w / v.

Sopropone T36 (sodium polycarboxylate) 0.5% w / v.

Antifoam FD (silicone antifoam agent) 0.1% w / v.

Rhodigel 23 (xanthan gum) 0.2% w / v.

Dichlorophene sodium solution, 40% w / w. 0.25% w / v

Water . ad 100% by volume

Example 3

A water miscible agent containing bromoxynil potassium salt was prepared from: Bromoxynil 25% w / v.

Potassium hydroxide 5.1% w / v

Tetrahydrofuryl alcohol 25% w / v.

Water ad 100% vol.%,

by mixing together a portion of the water, the tetrahydrofuryl alcohol, the bromoxynil and potassium hydroxide with heating and stirring, and then the volume was made up to 100% with water.

Example 4

An emulsifiable agent containing bromoxyniloctanoate was prepared from: Bromoxyniloctanoate containing 63.9% w / w. Phenolic acid equivalent 35.2% w / v. Atlox 4855 (mixture of anionic and nonionic surfactants) 3.75% w / v. Agrilan A (mixture of anionic

and nonionic surfactants) 3.75% w / v.

Solvesso 150 (aromatic C ₁₀ petroleum fraction) ad 100 vol.%,

by mixing together a portion of the aromatic C ₁₀ petroleum fraction, Atlox 4855, Agrilan A and the bromoxyniloctanoate with warming and stirring and then making the volume 100% with further C ₁₀ aromatic petroleum fraction.

Example 5

An aqueous suspension concentrate containing bromoxynilpheriol was prepared from: Bromoxynil 56.25% w / v.

Soprophor FL (arylphenol ethoxylate phosphate ester) 3.5% w / v.

Sopropon T36 (sodium salt of a polycarboxylic

acid) 0.3% w / v.

Ethylan BCP (nonylphenol / ethylene oxide condensation product containing 9 moles of ethylene oxide) 0.5% w / v.

- I U - ί, ΊΟ * Κ? Ο

Antifoam FD (silicone antifoam agent) 0.1% w / v.

Attagel 50 (swellable attapulgite clay) 2.0% w / v

Propylene glycol 5.0% w / v.

Water ad 100% by volume;

the components were intimately mixed and ground by pumping under pressure through a ball-fed mill.

Example 6

An aqueous suspension concentrate containing bromoxyniloctanoate and diflufenican (5.87: 1) was prepared from: Bromoxyniloctanoate containing

63.9% w / w Phenolic acid equivalent 35.2% w / v.

Arylan CA (calcium dodecylbenzenesulfonate,

70% solution in butanol) 2.0% w / v.

Synperonic NPE 1800 (nonylphenol

ethylene oxide / propylene oxide block copolymer) 3.0% w / v.

Solvess 200 (aromatic C ₁₀ / C, ₃ petroleum fraction) 6.0% w / v. Diflufenican 6.0% w / v.

Soprophor 3D33 (ethoxylated polyarylphenol phosphate, neutralized

with triethanolamine) 0.16% w / v.

Olin 10G (nonylphenol / glycidol 0.08% w / v.

Condensation product containing 10 moles of glycidol)

Antifoam FD (silicone antifoam agent) 0.2% w / v.

Attagel 50 (swellable attapulgite clay) 2.0% w / v

Ammonium chloride 5.0% w / v.

Water ad 100% by volume

The calcium dodecyl benzenesulfonate solution, the nonylphenol ethylene oxide / propylene oxide block copolymer, the aromatic C ₁₀ / C ₁₃ petroleum fraction, and the bromoxyniloctanoate were mixed together with heating and stirring. An aqueous suspension concentrate was then prepared by intimately mixing 40 vol.% With the diflufenican, the ethoxylated polyarylphenol phosphate neutralized with triethanolamine, the nonylphenol / glycidol condensation product, the silicone antifoaming agent, attapulgite clay, and ammonium chloride, and then finely grinding by pumping under pressure through a ball mill. The bromoxyniloctanoate solution previously prepared was then added to this suspension concentrate with stirring and the volume made up to 100% by the addition of water.

1.5 l of the resulting formulation were diluted in 200 l of water and sprayed after emergence onto 1 ha of winter wheat to eliminate Stellaria media, Viola arvensis and Veronica persica.

Example 7

A 10: 1 mixture was prepared by mixing in the 888 ml tank of Example 5 with 100 ml of the Example Example in a volume of 100 liters of water. The resulting spray liquid was applied to 1 ha of accumulated barley to control Polygonum convolvulus, Sinapis arvensis and Amaranthus retroflexus.

Example 8

Example 7 was repeated except that 50 ml of the agent of Example 2 was used and a 20: 1 mixture was prepared.

example

A 25 mixture was prepared by mixing in the tank of 444 ml formulation of Example 4 with 500 ml formulation of Example 2 in 300 l water. The resulting spray liquid was applied to 1 ha of spring wheat shortly after emergence to control accumulated and germinating Setaria viridis and Amaranthus retroflexus.

Example 10

A tank mix was prepared consisting of 600 ml formulation of Example 6 and 1800 ml of a stable aqueous solution containing potassium, sodium and dimethylamine salts of MCPA corresponding to 500 g / l 2-methyl-4-chlorophenoxyacetic acid and 200 l of water. This mixture was applied after emergence to 1 ha of winter wheat to control Stellaria media, Galeopsis tetrahit, Sinapis arvensis and Viola arvensis.

In the herbicide mixtures of the preceding examples, the urea herbicide may be replaced by another urea herbicide or a mixture of urea herbicides.

Claims (7)

- I - ^ HO Invention claim: A herbicidal composition characterized in that it comprises (a) 3,5-dibromo-4-hydroxybenzonitrile (bromoxynil) and / or 4-hydroxy-3,5-diiodobenzonitrile (loxynil) or an agriculturally acceptable salt or an agriculturally acceptable ester or a mixture thereof and (b) N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide (diflufenican) as active ingredient, together with a conventional diluent or carrier and / or surfactant. 2. Composition according to item 1, characterized in that it contains (a) and (b) in a weight ratio of 20: 1 to 2: 5. 3. Composition according to item 1 or 2, characterized in that it contains as active ingredient (a) an ester of bromoxynil and / or loxynil with a C ₄ to C ₈ alkanoic acid. 4. Composition according to item 3, characterized in that it contains as active ingredient (a) bromoxyniloctanoate or bromoxynil heptanoate. 5. Composition according to one of the items 1 to 4, characterized in that it additionally as active ingredient (RS) -2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid (diclofop), 4-chloro-2-methylphenoxyacetic acid ( MCPA) and / or (±) -2- (4-chloro-2-methylphenoxy) propionic acid (mecoprop) or an agriculturally acceptable salt or ester thereof. 6. Use of the agent according to one of the items 1 to 4, characterized in that it is used in an application rate of 100 to 500 g of acid equivalent (S.A.) / ha (a) and from 25 to 250 g / ha (b) used simultaneously, separately or sequentially for weed control in cereal crops. 7. Use of the agent according to any one of items 1 to 6, characterized in that the application rate of the additional active ingredient 500 to 1500 g Sa / ha for diclofop, 100 to 1500 g S.A. / ha for MCPA and 1000 to 2500 g S .A. / ha for mecoprop.