PL148016B1 - Herbicide - Google Patents

Description

The subject of the invention is a herbicide containing urea herbicide and N-(2,4-difluorophenyl)-2-(3-trifluoromethylphenoxy)nicotinamide of the presented formula. British patent specification No. 2087887A describes N-(2,4-difluorophenyl)-2-(3-trifluorophenoxy)nicotinamide as a herbicide used in agriculture before and after plant emergence. The wide use of urea herbicides and their mixtures, which poorly control certain weed species such as Galium aparine, Veronica hederifolia, Veronica persica and Viola arvensis, has led to an increase in the population of Galium aparine, Veronica and Viola so that they now constitute a serious problem in weedy cereal crops. As a result of searches and trials, it was found that the use of N-(2,4-difluorophenyl)-2-(3-trifluorophenoxy)nicotinamide N-(2-4-difluorophenyl)-2-(3-trifluoromethylphenoxy)nicotinic acid - hereinafter referred to as diflufenican - in combination with a urea herbicide extends the spectrum of action against Galium aparine, Veronica spp. and Viola spp. Thus, the above combination represents an important technical advance. Furthermore, it was unexpectedly found that the herbicidal action of the combination of diflufenican with a urea herbicide against certain weed species is greater than expected when applied pre- or post-emergence (e.g., as a pre- or post-emergence spray). This means that the herbicidal action of diflufenican with a urea herbicide shows an unexpected and significant degree of synergism. According to the definition of P.M.L. Tammes, Netherlands Journal of Plant Pathology, 70 (1964) pp. 73-80 in the work entitled "Isoboles, a graphic representation of synergism in pesticides", or according to the definition by L.E. Limpel, P.H. Schuldt and B.^Lamont, 1962, Proc. NEWCC 16;48~539 the synergistic effect is determined by the formula: 2 148 016 E - x + T - T55 in which E is the % inhibition of growth by the mixture of two herbicides at specific doses, X is the % inhibition of growth by herbicide A at a specific dose, Y is the % inhibition of growth by herbicide 3 at a specific dose, (the combination is synergistic when a greater than expected response is observed). Significant synergism against Galiura aparine and Avena fatua improves the reliability of killing. two of the most competitive weeds in cereal crops and leads to a significant reduction in the amount of active ingredient required for weed control. High levels of control of these species are desirable to prevent (a) yield losses due to competition or difficulties associated with harvesting and seed cleaning, and (b) unacceptable weed seed return to the soil. It should be noted that whenever reference is made in this specification to a urea herbicide, this refers to a urea herbicide such as N,N-dimethyl-N'-(4-(1-methylethyl)phenylurea), called isoproturon; N,N-dimethyl-N'-(3-chloro-4-methylphenylurea), called chlorotoluene; N-2-benzothiazolyl-N,N'-dimethylurea, called methabenzthiazuron; N-butyl -N'-(3,4-dichlorophenyl)-N-methylurea, called neburon, N'-(3,4-dichlorophenyl)-N-methoxy-N-methylurea, called linuron, or mixtures thereof. Preferred are mixtures of 2:1 to 1:2 by weight, especially 1:1, of isoproturon and neburob. The herbicidal composition according to the invention comprises (a) the urea herbicide as defined above and (b) deflufenican, in the form of a combined preparation for simultaneous use for killing weeds at their locus. The composition according to the invention may optionally comprise (a) the urea herbicide and (b) diflufenican in combination with a herbicidally acceptable diluent or carrier and/or surfactant. The composition according to the invention preferably contains components (a) and (b) in a weight ratio of 400:1 to 1:5, especially 70:1 to 2:1. The above-defined urea herbicide and diflufenican are usually used in the form of herbicidal formulations, i.e. in combination with homogeneously miscible diluents or carriers and/or surfactants suitable for use in herbicidal compositions, for example as given below. The application rates of the composition according to the invention can vary depending on the type of weeds, the composition used, the time of application, the climatic conditions and the grouping, and on the type of cereals if weed control is carried out in an area of developing cereals. When the composition according to the invention is used in an area of cereal crops, the application rate should be sufficient to kill weeds without significant permanent damage to the crop. Taking all these factors into account, generally, rates of 150 to 10 kg of urea herbicide and 25-750 g of diflufenican per hectare are used with good results. However, it should be borne in mind that, depending on the specific weed control problem, higher or lower rates may be used. Preferably, urea herbicide is used at rates of 500 g - 10 kg/ha and diflufenican at rates of 50 g - 750 g/ha. The agent according to the invention can be used for selective weed control, for example, pre- or post-emergence, for the control of the above-mentioned species by direct or indirect application, e.g., by direct or indirect spraying, to weed infestations that are used or are intended to be used for crops, e.g. cereals such as wheat, barley, oats, rye, maize and rice, soybeans, pole and dwarf beans, peas, alfalfa, cotton, peanuts, flax, onions, carrots, rapeseed, sunflowers, and permanent or sown pasture, before or after sowing the crop, or before or after crop emergence. For selective weed control in weedy areas, in the crop area or in the area where a crop is to be grown, e.g. such as the one mentioned above, doses of 150-3500 g/ha of urea herbicide and 25-250 g/ha of diflufenican are particularly suitable. Pre-emergence application is preferred. or a post-emergence herbicide comprising (a) a urea herbicide such as chlortoluron, isoproturon, linuron, methabenthiazuron and neburon or mixtures thereof, preferably in a weight ratio of 1-1 of isoproturon and neburon, and (b) diflufenican at rates of 500:3500 g/ha, preferably 500-2500 g/ha and 50-250 g/ha, respectively, in a weight ratio (a) to (b) of 70:1-2:1, preferably 50:1-2:1, for the control of a very wide range of annual broadleaf weeds and grasses in cereal crops, e.g. wheat, barley, oats and rice, without significant permanent damage to the crop, the combined use of both components giving an effect on both In accordance with this feature, it is advantageous to use the herbicide according to the invention in winter cereals. In the method described above, it is advantageous to use in combination (a) a urea herbicide such as chlorotoluron, isoproturon and neburon or mixtures thereof in a weight ratio of 2:1 to 1:2 and (b) diflufenican in a weight ratio of component (a) to (b) of 20:1 to 4:1. The combination of urea herbicide and diflufenican can also be used for killing weeds, especially those mentioned below, both pre-emergence and post-emergence. In gardens, orchards, and other wooded areas, such as forests and parks, and in plantations such as sugarcane, oil palm, and rubber plantations. For this purpose, the product can be applied directly or indirectly (e.g., by direct or indirect spraying) to weeds or to the soil where they are expected to emerge, before or after planting trees or plantations, at rates of 1000–5000 g of urea herbicide and 100–500 g of diflufenican per hectare. A product containing urea herbicide and diflufenican can also be used to kill weeds, especially those listed below, in areas where no crops are present but weed control is desired. Examples of such non-crop areas include airports, industrial areas, railways, river banks, and roadsides. roads, water and irrigation channels, scrub and fallow land, or uncultivated land, especially where weed control is desired to reduce the risk of fire. When used for this purpose, where complete weed control is often desired, the active compounds are usually applied at higher rates than in cultivated areas. The exact rate will depend on the nature of the vegetation being treated and the desired effect. Particularly suitable for this purpose for pre- or post-emergence application, preferably before emergence by direct or indirect means (hp. by direct or indirect spraying), are rates in the range of 2500 g to 10 kg of urea herbicide and 200-750 g of diflufenican per hectare. The term "pre-emergence application" means application to the soil in which the weed seeds or seedlings are already established. present, before the weeds appear on the soil surface. The term "post-emergence application" is understood to mean application to the aerial parts or exposed parts of weeds that have germinated from the soil. The term "foliar action" is understood to mean the herbicidal action produced by application to the aerial parts or exposed parts of weeds that have germinated above the soil surface. The term "residual action" is understood to mean the herbicidal action produced by application to the soil in which weed seeds or seedlings are present before they emerge on the soil surface, as a result of which the seedlings present at the time of application or which germinate after application from seeds present in the soil are destroyed. The weeds that can be controlled by the composition according to the invention are: 016 jace: Veronica persica, Veronica hederifolia, Stellaria media, Lamium purpureum, Lamium amplexicaule, Aphanes arvensis, Galium aparine, Alopecurus myosuroides, Matricaria incdora, Matricaria matricoides, Anthemis arvensis, Anthemis cotula, Papaver rhoeas, Poa annua, Apera spica venti, Phalaris paradoxa, Phalaris minor, Avena fatua, Lolium perenne, Lolium multiflorum, Broraus sterilis, Poa trivialis, Spergula arvensis, Cerastium holosteoides, Arenaria serpyllifolia, Silene vulgaris, Legousia hybrida, Geranium molle, Geranium dissectum, Srysimum cheiranthoides, Descurainea sophia, Kontia perfoliata, Anagallis arvensis, Myosotis arvensis, Chenopodium album, Polygonum aviculare, Polygonum convolvulus, Galeopsis tetrahit, and Chrysanthemum segetum. In accordance with traditional practice, a mixture may be prepared before use by combining in a tank the separate formulations of the individual ingredients comprising the herbicide according to the invention. The following tests illustrate the invention: Test 1. The following greenhouse tests demonstrate the synergistic action of a combination of isoproturon and diflufenican in the control of certain weed species. 25 treatments were carried out at a wide range of doses, i.e. 0, 125, 250, 500 and 1000 g a.i. (active ingredient) per hectare of isoproturon plus diflofenican 0, 125f 250, 500 and 1000 g a.i./ha as indicated in the table below. /- isoproturon g a.i. /ha Diflufenican Treatment g a.i. /ha (1) 0 (2) 125 (3) 250 (4) 500 (5) 1000 I (6) | 125 (7) ! 125 I + 125 : w | 125 + 250 (9) 125 + 500 (10) 125 + 1000 I (11) I 250 ' ^12) 250 | + ! 125 i TC) 250 + 250 (14) 250 + 500 (15) I 250 + 1000 (16) 500 I (17) i 500 i + j 125 (18) 500 + 250 (19) 500 + 500 (20) l 500 + 1000 I ^ I ! 1000 and (22) I 1000 + [ 125 (23^ I I 1000 + I 250 (24) 1000 + I 500 (25) 1000 + I 1000 All treatments were prepared in the appropriate amount of water by mixing 50% (by weight) volume of an aqueous suspension of isoproturon concentrate (commercial product) and diflofenican prepared as an experimental wettable powder (Example 1) containing 50% by weight of the active ingredient, to obtain the above doses/ha in a spray volume of 260 l/ha. All the above tests were carried out using a laboratory sprayer on a Spraying Systems Teejet SS 8003E operating at a pressure of 0.2 MPa. Treatments consisted of 10-15 Galium aparine or Avena fatua seeds sown at a depth of 1-2 cm in sandy loam soil in 9 cm diameter plastic pots. Three replicate pots were used for each treatment, arranged alternately. After treatment, the pots were moistened by watering from above and irrigation from below. Visual assessment of weed control was performed 21 days after treatment using a 0-10 scale, where 0 indicates no effect and 10 indicates 100% control compared to untreated plants. Average % weed control was calculated for each species and summarized below for each of the 25 treatments given above; the position in the table corresponds to the treatment given in the previous table. Galium Avena 0 47 70 80 100 0 80 90 100 100 0 87 100 100 100 0 90 100 100 100 0 93 1 100 100 100 I ° I 50 80 90 95 43 70 90 97 100 50 83 93 97 100 67 90 97 100 100 70 93 I 100 100 100 | From the above, the herbicidally effective dose at 90°C (ED90) in g a.i./ha calculated for diflufenican and isoproturon alone and diflufenican + 125, 250 g, 500 g and 1000 g isoproturon is respectively: Galium (ED90 g/ha) Diflufenican alone Diflufenican + 125 g/ha isoproturon Diflufenican + 250 g/ha isoproturon Diflufenican + 500 g/ha isoproturon Diflufenican + 1000 g/ha isoproturon Isoproturon alone - inactive • 484 209 ! j 136 I 125 106 Avena (ED90 g/ha) Diflufenican alone Diflufenican + 1?5 g/ha isoproturon 1 Diflufenican + 250 g/ha isoproturon Diflufenican + 500 g/ha isoproturon Diflufenican + 1000 g/ha isoproturon Isoproturon alone ¦ 538 275 199 122 107 I 5668 The values given above were used to plot the isobole ED90 for a) the so-called single-acting (Tammes p. 74 fig. 1) case of Galium, which was resistant to isoproturon, shown in the attached fig. 1 and b) the so-called double-acting (Tammes p. 75 fig. 2) case of Avena® when both compounds were active, shown in the attached fig. 2. 1 and Fig. 2 clearly demonstrate type II and III isobols, respectively, characteristic of synergism* ED90 values were used for the construction of isobols because 90# represents the desired level of weed control in agricultural situations (see isobols for amitrole atrazine synergism, Tammes, Fig. 5 p. 77)*6 148 016 Trial 2. A similar trial as the previous one was carried out with chlorotoluron and diflufenican on Avena fatua, obtaining the following results: BP 90 (g/ha) 586 / 450 300 95 75 2186 These results, plotted in the attached Fig. 3 for the so-called double-acting (Tammes 75 Fig. 2) clearly show the type III isobols characteristic of synergism. Trial 3* Greenhouse trial showing the nature of biological synergism between neburon and diflufenican. 43 treatments were carried out at a wide range of doses, i.e. 0 to 125, 250, 500, 1000, 2000 and 4000 g of active ingredient per hectare of neburon plus diflufenican 0, 31.25, 62.5, 125, 250, 500 and 1000 g a.i./ha as indicated in the table below. neburon g a.s./ha diflufenican alone Diflufenican + 125 g/ha chlortoluron Diflufenican + 250 g/ha chlortoluron Diflufenican + 500 g/ha chlortoluron Diflufenican + 1000 g/ha chlortoluron alone chlortoluron p.Treatment diflufenican g a.i. /ha! i ^I 0) 0 | <8) I 31.25 i- (u).- 62.5 (20) 125 (26) 250 (32) 500 (38) 1000 (2) 125 (9) 125 + 31.25 ¦ (15) 125 62.5 (21) 125 • + 125 (27) 125 + 250 (33) 125 ¦ + 500 (39) 12* + 1000 I (3) 250 ! to) | 250 I + ! 31.25 ! (16) ; 250+ ; 62.5! (22) 250 + 125 (28) 250 + 250 (34) 250 + I 500 (40) 250 + 1000 I (4) 500 (11) ! 500 i + I -31^25 i (17) ! 500 62.5 ; (23) , 500 + 125 _(29) 500 + 250 (35) 500 + 500 (41) I 500 + 1000 | (5) 1000 j (12) I 1000 + j 31.25 (18) 1000 + ! 62.5 (24) 1000 + 125 (30) 1000 + 250 (36) 1000 500 \ (42) 1000 I + 1000 I (6) I 2000 ! (13) | 2000 31.25 (19) ! 2000 | 62.5 (25) 2000 + i 125 i (31) 2000 • + 250 (37) 2000 + 500 (43) I 2000 + i 1000 I (7) i 4000 I 1 ! ; i J All treatments were made in appropriate volumes of water to obtain the above dose/hectare in a spray volume of 290 l/ha. Neburon was prepared as an experimental wettable powder containing 25% by weight of the active ingredient (Example IX). Diflufenican was prepared as an experimental aqueous concentrate of 148,016 suspension containing 50% by weight of the active ingredient (Example II). All treatments were carried out using a laboratory sprayer mounted on a Teejet SS 8003E Spraying Systems operating at a pressure of 0.5 MPa. Treatments were carried out after emergence of Galium aparine at the umbel stage. The plants were grown in non-sterile sandy loam soil in square 7 cm plastic pots. Four replicate pots were used for each treatment, which were arranged alternately in the greenhouse. After treatment, the pots were watered from the top and irrigated from the bottom. Visual assessment of weed control on a scale of 0-100 was performed 22 days after treatment. The mean % weed control was calculated for each treatment and species. From the above, the herbicidally effective dose in 905© (ED90) in g a.i./ha was obtained, calculated for diflufenican alone, neburon alone and for diflufenican + 125, 250, 500, 1000 and 2000 g a.i./ha neburon, respectively: Galium (ED 90 g/ha) Diflufenicansam 459 Diflufenican + 125 g/ha neburon 218 Diflufenican + 250 g/ha neburon 127 Diflufenican + 500 g/ha neburon 49 Diflufenican + 1000 g/ha neburon 22 Diflufenican + 2000 g/ha neburon 15 Samneburon 5185 ED 90 values was used to plot the so-called double-acting isobole for Galium shown in Fig. 4. This type III isobole clearly shows synergism (Tammes, p. 75, Fig. 2). Test 4. Greenhouse test showing the nature of biological synergism between linuron and diflufenican. A similar experiment to that described in Example 3 was carried out with linuron and diflufenican using 0, 250, 500, 1000 and 2000 g a.i./ha of linuron as a 50% by weight wettable powder (commercial product) plus diflufenican at 31, 125, 500 and 1000 g a.i./ha*. From these results the following ED 90 values were calculated. ED 90 g /ha Diflufenican alone 684 Diflufenican + 250 g/ha linuron 201 Diflufenican + 500 g/ha linuron 69 Diflufenican + 1000 g/ha linuron below 31 Diflufenican + 2000 g/ha linuron below 31 These results, plotted in Fig. 5 given in the appendix for the so-called double action (Tammes, p. 75, Fig. 2), clearly show the type III isoboles characteristic of the synergism. Trial 5 Greenhouse trial showing the nature of biological synergism between diuron and diflufenican. A similar experiment to that described in Example 3 was carried out with diuron and diflufenican using 0 and 187.5 g a.a./ha of diuron in the form of 80% by weight wettable powder (commercial product) plus diflufenican at rates of 31, 63, 125, 250, 500 g a.i. /ha. The observed weed control results were compared with the expected results using Limpel's formula: E « X + Y - -« XY T558 148 016 Control 0 I 31 63 125 250 500 0 Observed - 43 68 75 83 85 Diuron 60 93 100 100 100 99 g/ha 187.5 Expected - 78 87 89 93 94 Diflufenican g/ha Since the observed responses to the mixtures were higher than the expected results, the combinations were clearly synergistic. Trial 6. The effectiveness of these synergistic mixtures for a wide range of weeds in cereal crops was demonstrated in a series of small-plot trials where the mixtures were compared diflufenican (Example II) and isoproturon with isoproturon alone. Treatments were applied pre- and post-emergence in triplicate on alternating plots of 6 m x 3 m in a field containing a total of 21 plots, at a volume of 141 l/ha using a mechanical small-plot sprayer fitted with 6 x 80015 Spraying Systems Teejet sprayers. The mixtures were prepared by spraying the plots with each component separately, a few minutes apart (i.e., at a total volume of 282 l/ha). Weed control was assessed after 3 months by counting the number of weeds in each plot in 2 x 0.5 m squares. Crop condition was assessed for any visually noticeable phytotoxicity on a scale of 0 - 100, where 0 indicates no damage and 100 indicates 100% destruction. The results are presented in Table 1 below. Table 1 Average % weed control 1 j Treatment 1 Alopecuru3 myosuroides I Poa annua Galium aparine i Veronica persica Veronica hederifolia j Viola arvensis Lamium purpureum Stellaria media Matricaria inodora I Isoproturon 2000 g/ha I (a) 2 I 93<5 84(5) 31(4) 24(6) 13(D 26(5) 31(2) 83(6) 99(3) I | (b) 3 | 88<*) ' - 0(2) 60<+ , — - - 100(2) | 100(2) and Isoproturon 1500 g/ha + diflufenican 125 g/ha I (a) 4 W5* 99(5) 83(*) 100(6) ioq(1) 98(5) , 100(2) I 100(6) 100(3) ! (b) 5 93<5) — I 86(2) 10Q<*) — - - 100<2 100<2 Isoproturon 1500 g/ha + diflufenican | 250 g/ha | (a) 6 100(5) I o I i 7 93(3) I 100(5) j - ' I 99(4) 100(6) 100(1) 95(5) 99(2) 100(6) I 100(3) ! 99(* ioo(4) I • - 100(2) 100(2)148 016 9 continued from table 1 I and Papaver rhoeas | Aphanes arvensis barley * wheat* I 2 100<1 ioo(1 2(4) 1<6 j I 3 \ 2<4) ,(2) 4 100<1 ioo(1 4(5) 2(6) i " 5~^ ' i ^(4) iw r c j ioo(1 100(1) 8(4) 5 (6) i 7 1 i ' 4<* I 2(2) I (a) - before emergence (b) - after emergence The indicator in brackets gives the number of examined cases, the dash means no examination * average % phytotoxicity to crops (the highest Trial 7. The effectiveness of these synergistic mixtures on a wide range of weeds in cereal crops was demonstrated in a series of small-plot trials comparing single-tank mixtures of diflufenican (Example II below) and chlorotoluron with diflufenican alone. Treatments were applied pre-emergence in triplicate in alternating 6 m x 3 m plots at six different locations in the field at a volume of 261 l/ha using a mechanical small-plot sprayer fitted with 6 x 8004 Spraying Systems Tee Jets. Weed control was assessed in spring after the autumn application by counting weed numbers in 3 x 0.5 m squares within the plot. Crop condition was assessed for any visible phytotoxicity on a scale of 0 - 100, where 0* means no damage and 100 means 100# destruction. The results are presented in Table 2 below. Table 2 Average % weed control Treatment Anagallis arvensis Aphanes arvensis Arenaria serpyllifolia Chrysanthemum segetum | Lamium araplexicaule Papaver rhoeas Raphanus raphanistrum Stellaria media Katricaria inodora Veronica persica winter wheat * barley * rice * Chlortoluron 1500 g/ha + diflufenican 62.5 g/ha ioo(1 100<1 ioo(1 99(1) 99(1) 99(2) 99(1) 99(3) 99(2) 99(2) 0<1 0^ Diflufenican 125 g/ha W1* W1* 100<1 0<1 99(D 72(2) 100<1 99(3) 99(2) 99(2) o<1 3.7<* o<1 Index in brackets = number of cases examined x average % phytotoxicity in crops (highest recorded).10 148 016 Trial 8. Field trials were carried out in Belgium using a tank-mixed mixture of diflufenican (Example II below) with a 1:1 mixture of isoproturonurneburone or metabenzthiazuronene. Treatments were carried out in autumn before emergence, two replicates on 30 m2 plots, to control a wide range of broadleaf weeds and grasses in winter wheat and winter barley, at a volume of 500 l/ha, using Hand duster. Weed control was assessed in the spring following the autumn spraying. Phytotoxicity to the crops was recorded during the winter and spring, and the maximum recorded damage is given in Table 3 below. Table 3 Average % phytotoxicity Treatment Alopecurus myosuroides Poa annua Matricaria inodora Stellaria media Galium aparine Veronica spp Maximum recorded phytotoxicity to wheat or barley Wheat Index in parentheses = number of appearances. These trials clearly demonstrated the broad spectrum of weed control, including Galium aparine, veronica, and Viola, achieved by the mixtures. A composition according to the invention comprising components (a) and (b) as defined above, in a weight ratio of component (a) to (b) of 400:1 - 1:5, preferably in The composition is preferably homogeneously dispersed, e.g. in a weight ratio (a) to (b) of 70:1 - 2:1 and more preferably in a weight ratio (a) to (b) of 20:1 - 4:1, preferably homogeneously dispersed, with one or more herbicidally compatible diluents or carriers and/or surfactants (e.g. diluents or carriers of the usual type or surfactants which are suitable for use in herbicides and which can be used with the urea herbicide and diflufenican). The term homogeneously dispersed is used in relation to compositions in which the urea herbicide and diflufenican are dissolved in other ingredients. The term herbicides is used in a broad sense and includes not only ready-to-use herbicidal compositions but also concentrates which must be diluted before use. Preferably, the compositions contain from 0.05 to 90% by weight of the urea herbicide and diflufenican. The herbicidal compositions may contain both a diluent or carrier and a surface-active agent (e.g., a wetting, dispersing, or emulsifying agent). The surface-active agents used in the compositions according to the invention may be of the ionic or nonionic type, for example sulphoricinoleates, quaternary ammonium derivatives, products based on ethylene oxide condensates of nonyl- or octyl-phenols, or anhydrosorbitan esters of carboxylic acids, which are made solubilized by etherification of the free hydroxyl groups. Diflufenican 125 g/ha + Neburon 800 g/ha + Isoproturon 800 g/ha 95(3) 100<1 ioo(2 100<3 ioo(1 100(1 diflufenican 200 g/ha + metabenzthiazuron 1750 g/ha 95(4) 99 (1) 100<5) 100<* 97(2) 100<1 8 1Q(4)148 016 11 sulfuric acid esters of ethylene oxide, alkali metal or alkaline earth metal salts or esters of sulfuric acid and sulfonic acids such as dinonyl- and dioctyl-sodium sulfonic acid succinates and alkali metal and alkaline earth metal salts of high molecular weight sulfonic acid derivatives such as sodium and calcium lignin sulfonate. Examples of suitable solid diluents or carriers are aluminosilicate, talc, calcined magnesium oxide, diatomaceous earth, tricalcium phosphate, powdered cork, an adsorbent such as carbon black and clays such as kaolin and bentonite. A solid herbicide, e.g. dusts, granules or wettable powders, is preferably prepared by grinding the urea herbicide and diflufenican with solid diluents or by impregnating solid diluents or carriers with solutions of the urea herbicide and diflufenican in volatile solvents, evaporating the solvent and optionally grinding the product thus obtained to a powder. A granular preparation can be prepared by absorbing the urea herbicide and diflufenican (dissolved in volatile solvents) onto solid diluents or carriers in the form of granulation and evaporation of the solvents, or by granulating a powdered preparation in the form described above. Solid herbicides, especially wettable powders, may contain wetting or dispersing agents (for example of the type described above), which may also, when in solid form, serve as diluents or carriers. Liquid compositions according to the invention may be in the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions, which may contain a surface-active agent. Suitable liquid diluents for preparing liquid compositions are water, acetophenone, cyclohexanone, isophorone, toluene, xylene, and mineral, animal and vegetable oils and mixtures thereof. Diluents. Surface-active agents used in liquid formulations may be of the ionic and non-ionic type, for example as described above, and may, when in the liquid state, serve as diluents or carriers. Wettable powders and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates where the diluent or carrier is an oil, to give ready-to-use compositions. Alternatively, liquid compositions of urea herbicide and diflufenican may be used in the form of self-emulsifying concentrates containing the active substances dissolved in emulsifying agents or solvents containing emulsifying agents. Emulsifying agents that are homogeneously miscible with the active substances. Usually, adding water to such concentrates produces ready-to-use compositions. Liquid concentrates in which the diluent or carrier is an oil can be used without further dilution by electrostatic spraying. The herbicidal composition according to the invention may also optionally contain conventional auxiliaries such as binders, protective colloids, thickeners, penetrating agents, stabilizers, binders, anti-caking agents, dyes and corrosion inhibitors. The auxiliaries may also serve as carriers or diluents. In a preferred embodiment, the composition according to the invention is an aqueous suspension concentrate that contains 10-70% by weight/volume of the urea herbicide and diflufenican, 2-10% by weight/volume of the urea herbicide and diflufenican, weight/volume of surfactant, 0.1-5% weight/volume of thickener and 15-87.9% by volume of water; a wettable wettable powder which comprises 10-90% by weight of the urea herbicide and diflufenican, 2-10% by weight of surfactant and 10-88% by weight of a solid diluent or carrier; a liquid water-soluble concentrate which comprises 10-30% by weight/volume of the urea herbicide and diflufenican, 5-25% by weight/volume of surfactant and 45-85% by volume of a water-miscible solvent, e.g. dimethylformamide; a liquid, emulsifiable/12 148 016 suspension concentrate which contains 10-70% by weight/volume of urea herbicide and diflufenican, 5-15% by weight/volume of surfactant, 0.1-5% by weight/volume of thickener and 10-84.9% by volume of organic solvent; granules which contain 2-10% by weight of urea herbicide and diflufenican, 0.5-2% by weight of surfactant and 88-97.5% by weight of granular carrier; and a suspension concentrate which contains 0.05-90% by weight/volume and preferably 1-60% by weight/volume of herbicide urea herbicide and diflufenican, 0.01-10% by weight/volume and preferably 1-10% by weight/volume of surfactant and 9.99-99.94% and preferably 39-98.99% by volume of organic solvent, the composition according to the invention comprising the urea herbicide and diflufenican can be used in combination with, preferably homogeneously dispersed therein, one or more other pesticidal compounds and optionally one or more homogeneously miscible pesticidally acceptable diluents or carriers, surfactants and conventional auxiliaries as described above. Examples of other pesticidally active compounds which can be used in combination with the herbicide according to the invention are: of the invention, for example in order to increase the range of weed species destroyed, are alachlor (C-chloro-2,6-diethyl-N-(methoxymethyl)acetanilide), asulam (methyl 4-aminobenzenesulfonyl)carbamate, alloxydim Na, sodium salt 2-(l-al- lyloxya!ainobutylidene)-5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione, atrazine /~(2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine/, barban /4-chlorobut-2-y-nyl N-(3-chlorophenyl)-carbamate/, benzoylprop-ethyl £ N-benzoyl-N-(ethyl 3,4-dichlorophenyl-2-arainopropionate), bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) (preferred), butachlor (N-(butoxymethyl)-o[-chloro-2,6-diethylacetanilide), butylate (N,N-dlybutyl) S-ethyl ocarbamate/, carbetamide / D-N-ethyl^2-(phenylcarbamoyloxy)-propionamide/, chlorphenpropmethyl /methyl 2-chloro-2-(4-chlorophenyl)-propionate/, chlorpropham /n-('v- chlorophenyl)isopropyl carbarate/, cy janazine/2-chloro-4-(l-cyano-1-methylethylau^- no)-6-ethylamino-1,3» 5-triazine/, cyclonate / (thiocarbamate)N*-cyclohexyl-N-ethyl- -S-ethyl/, 2,4-D /2,4-dichloropropionic acid/, 2,4-DB /4-(2,4-dichlorophenoxy)butyric acid/, dalapon/"acid 2,2-dichloropropionic acid/, desnedifam /3-(ethoxycarbonylamino)phenyl N-phenylcarbamate/, diallate/3-2,3-dichloroallyl-N,N-diisopropylyl (thiocarbamate), dicamba •_ 3f 6-dichloro-2-:netoxybenzoic acid, dichlorprop £ acid (+)-2-(2,4- -dichlorophenoxy)propionic acid, diphenzoauate (1,2-dimethyl-3,5-diphenylpyrazolium salts), dinitraraene and N1,N1-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine, EPTC (α,N-dipropyl(S-ethyl thiocarbamate), ethofusate (2-ethoxy-2,3-dihydro-3,3-dimethyl-benzofuran-5-yl methylsulfonate), flamprop-isopropyl ((+)-2-(N-benzoyl-3-chloro-4-fluoroanilino)propionate), flamprop-methyl ((+)-2-(N-benzoyl-3-chloro-4-fluoroanilino)-methylpropionate), ioxynil / 4-hydrokay-3,5-diiodobenzonitrile/ (preferred), MCPA /4-(4-chloro-2-methylphenoxy)butyric acid/, mecoprop /^(+)-2-(4-chloro-2-methylphenoxy)propionic acid/ (preferred), metamitron Z 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one/, metribuzin /4-amino-6-t-butyl-3-(methylthio)-1,2f4-triazin-5(4H)-one/, molinate £ N,N-hexamethylene(3-ethyl thiocarbamate), oxadiazon l 3-(2,4-dichloro-5-isopro- phenmedipham (3-(methoxycarbonylamino)phenyl)-N-(3-methylphenyl)carbamate), prometryne (~4,6-bisisopropylamino-2-methylthio-1,3,5-triazine), propachlor (oC-chloro-N-isopropylacetanilide), propanil (3,4-dichloropropioanilide), propham (isopropyl N-phenylcarbamate), pyrazone 5-amino-4-chloro-2-phenylpyridazin-1,3,5-one/, simazine / 2-chloro-4,6-bisethyl-amino-1,3,5-triazynaj7, TCA ^trichloroacetic acid/, thiobencarb / N,N-diethylthiolcarbamate S-(4-chlorobenzyl)/, triallate /^N,N-di-isopropyl(thiocarbamate) S-2,3,3-tri-chloroallyl/ and trifluralin /"2,6-dinitro-N,N-dipropyl-4-trifluoromethylanilinay, 148 016 13 insecticides, e.g. carbaryl ^N-naphthyl N-methylcarbamate, synthetic pyrethroids, e.g. permethrin and cypermethrin, and 2,6-dimethyl-4-tridecyl-morpholine, methyl N-(1-butylcarbamoylbenzimidazol-2-yl)carbamate, 1,2-bis-(3-methoxycarbonyl-2-thioureido)benzene, 1-carbamoyl-3-(3,5-dichlorophenyl)isopropylhydantoin and 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one. Other biologically active materials which can be used together with the agent according to the invention are plant growth regulators, e.g. butylamino acid, (2-chloroethyl)triethylammonium chloride and 2-chloroethanephosphonic acid, or artificial fertilizers, e.g. those containing nitrogen, potassium and phosphorus, and trace elements essential for proper plant development, e.g., iron, magnesium, zinc, manganese, cobalt, and copper. Pesticides and other biologically active substances used together with the agent according to the invention, for example, those mentioned above, of acidic nature, may optionally be used in the form of conventional derivatives, for example, esters or salts of alkali metals or alkaline earth metals. The herbicide according to the invention, as a manufactured product containing the urea herbicide and diflufenican, or preferably as the herbicide described above, and preferably as a herbicidal concentrate which must be diluted before use, containing the urea herbicide and diflufenican in a container of the above-mentioned urea herbicide and diflufenican or the said agent, may be supplemented by instructions permanently attached to the above. container, specifying the manner in which the urea herbicide and diflufenican or the herbicide contained therein is to be used to kill growing weeds. Containers of the type traditionally used for storing solid chemicals at normal ambient temperatures and herbicides, especially in concentrated form, are usually used, for example metal canisters, and drums, which may be internally varnished or plastic-lined, glass and plastic bottles, and, when the contents of the container are in solid form (for example granular herbicide), boxes of e.g. cardboard, plastic and metal, or bags may be used. Containers with a capacity appropriate to the quantity of active ingredients or herbicidal composition sufficient to treat at least 0.4 hectares of field to kill growing weeds, but not exceeding a size convenient for The instructions are usually attached to the container, for example printed directly on it or on a label or sticker. The instructions usually state that the contents of the container, after dilution if necessary, are to be used to control growing weeds at rates of 150 g - 10 kg of urea herbicide and 25 - 750 g of diflufenican per hectare, in the manner and for the purpose specified in these instructions. A feature of the composition according to the invention containing a combination of (a) a urea herbicide, preferably the one described above, and (b) diflufenican is the possibility of simultaneous use of herbicidal active ingredients for weed control. The following examples illustrate the composition according to the invention. Example I. A composition was prepared from the following ingredients. in the form of a wettable powder: Diflufenican 50% by weight Nekal BX (sodium alkylnaphthalene sulfonate) Sodium lignosulfonate 3% by weight Sopropon T36 (sodium polycarboxylate) 0.5% by weight Hymod AT (polymer clay) to 100% by weight. Example II. An aqueous suspension concentrate was prepared from the following ingredients: Diflufenican 50% by weight/volume 14 148" 016 Qf 5% by weight/volume Etylan BCP (condensate of nonylphenol and ethylene oxide containing 9 moles of ethylene oxide per mole of phenol) Soprofor FL (triethanolamine salt of ethoxylated polyarylphenol phosphate) Sopropon T 36 (sodium polycarboxylate) antifoam Antifoam FD (silicone emulsion) Rhodlgel 23 (xanthan gum) 40% by weight sodium dichlorophene solution Water Example ingredients: Isoproturon Diflufenican Arylan S (sodium dodecylbenzenesulfonate) Dajpvan No. 2 (sodium lignosulfonate) Aerosil (micro-sized silica) Celite PF (synthetic magnesium silicate carrier) by mixing and grinding the mixture in a hammer mill to obtain a wettable powder which can be diluted with water and applied at a rate of 6.25 kg ha in 200 litres of liquid spray per hectare to control grass and broadleaf weeds including Avena fatua and Galium aparine, by pre- or post-emergence application in wheat crops Example IV. An aqueous suspension concentrate (4:1) was prepared from the following ingredients: 10% by weight/volume 0.5% by weight/volume 0.1% by weight/volume 0.2% by weight/volume 0.25% by weight/volume to 100% by volume. III. A wettable powder (20:1) was prepared from the following ingredients: 40% by weight 2% by weight 2% by weight 5% by weight 5% by weight 46% by weight Isoproturon Diflufenican Etylan BCP (nonylphenol-ethylene oxide condensate containing 9 moles of ethylene oxide per mole of phenol) Antifoam PD (silicone emulsion) Pluronic L62 (ethylene oxide-propylene oxide block copolymer) Sopropon T36 (sodium salt of a polycarboxylic acid) Attagel 50 (swellable attapulgite clay) Water, made up to 100% by volume by mixing thoroughly and grinding in a ball mill within 24 hours. The concentrate so obtained was dispersed in water and applied at a rate of 2 l/ha before and after barley emergence to control a wide range of broadleaf weeds, including Galium aparine. Example V Water-dispersible granules (20:1) were prepared by granulating the ingredients used in Example III with water in a pan granulator of 0.1-2 mm diameter. The granules were then dispersed at a dose of 6.25 kg in 200 litres 40% w/v 10% w/v 2% w/v 0^5% w/v 2 ^w/v 0.5% w/v 0.5% w/v H8016 -.5 water per hectare to control a wide range of grasses and broadleaf weeds. For pre- and post-emergence application in winter wheat* Example VI. Prepared Emulsifying suspension concentrate (50:1) with the following ingredients: Isoproturon 50% w/v Diflufenican 1% w/v Etylan TU (nonylphenol and ethylene oxide condensate containing 10 moles of ethylene oxide per mole of phenol) Bentone 38 (organic derivative of special magnesium montmorillonite used as a thickener) Aromasol H (aromatic solvent consisting mainly of isomeric trimethylbenzene) to 100% by volume by mixing thoroughly and ball milling for 24 hours. The emulsifiable suspension concentrate thus obtained can be diluted with water and used at a rate of 5 liters of emulsifiable suspension concentrate in 100 liters of liquid spray per hectare to destroy Alopecurus myosuroides, Viola arvensis and Veronica persica before the emergence of cultivated winter wheat. Example VII. A 1:2 mixture of (a) the aqueous suspension concentrate of diflufenican (Example II) and 50% by weight of a commercially available isoproturon preparation (b) was prepared in a tank by adding 0.5 liter of (a) to 1 liter of (b) in 200 liters of water. The resulting liquid spray was applied to 1 hectare of wheat shortly after germination of the crop and weeds to kill Galium aoarine, viola 'arvensis, Yeronica hederofolia, Veronica persica, Stellaria medli and Katricaria inodora. Example VIII. A 1:70 mixture of aqueous (a) diflufenican suspension concentrate (Example II) and 50% by weight of a commercially available chlortoluron preparation (b) was prepared in a tank by adding 0.1 liter of concentrate (a) to 7 liters of preparation (b) in 200 liters of water. The resulting spray liquid was applied to 1 hectare of wheat shortly after germination of the crop and weeds to kill Avena fatua, Alopecurus myosuroides, Stellaria media, Matricaria inodora, Veronica persica and Viola arvensis. Example IX. A wettable powder was prepared from the following ingredients: Neburon 25% by weight Nekal BX (sodium alkylnaphthalenesulfonate) 10% by weight Sodium lignosulfonate 3% by weight Sopropon T 36 (sodium polycarboxylate) 0.5% by weight Silica filler to 100% by weight Example X. A mixture of (a) the aqueous suspension concentrate of diflofenican (Example II) and 50% by weight of a ready-made commercially available isoproturon:neburon preparation (1:1) was prepared in a tank in a ratio of (a):(b) 1.25:16 by adding 0.25 litre of (a) to 3.2 kg of (b) in 200 litres of water. The resulting spray liquid was applied to 1 hectare of wheat shortly after the crop and weeds had emerged to destroy Avena Fatua, Alopecurus myosuroides, Stellaria media, Matricaria inodora, Yeronica persica and Viola arvensis. Example XI. A tank mixture (1:8.75) of (a) an aqueous suspension concentrate of diflufenican (Example II) and 70% (by weight) of a commercially available methabenzthiazuron formulation (b) was prepared by adding 0.4 liter of (a) to 2.5 kg of (b) in 200 liters of water. The resulting spray liquid was applied to 1 hectare of wheat shortly after germination of the crop and weeds to kill Avena fatua, Aiopecurus myosuroides, Stellaria media, Matricaria inodora, Veronica persica and Yiola arvensis. In the above examples, in the formulations containing mixtures of components (a) and (b), the mentioned urea herbicide can be replaced by another urea herbicide or 1. A herbicidal agent, characterized in that it comprises (a) a urea herbicide such as N-(N-dimethyl-N"-A-C 1-methylethyl)phenylurea, N,N-dimethyl-N*-(3-chloro-4-methylphenyl)urea, N-S-benzothiazolyl-N*-dimethylurea, N-butyl-N*-(3,4-dichlorophenyl)-N-methylurea, N'-(3,4-dichlorophenyl)-N-methoxy-N-methylurea or mixtures thereof, and (b) N-(2,4-trifluorophenyl)-2-(3-trifluoromethylphenoxy)nicotinamide, optionally in combination with a herbicidally acceptable diluent or carrier and or surfactant, in the form of a combined 2. The agent according to claim 1, characterized in that it contains component (a) and (b) in a weight ratio of 400:1 - 1:5. 3. The agent according to claim 1, characterized in that it contains component (s) and (b) in a weight ratio of 70:1 - 2;1 *148 016 1000 ED 90 Izobola for Galium aparine isoproturon g.s.a./ha 200 300 400 ditlutenican g.s.a. /ha 600 FIG. 1 ED 90 •• Izobola for Avena fatua zoproturon g.s.a./ha 100 200 300 /CO ditlufenican g.s.a./ha 500 600 FIG.2148 016 2500 ED 90: Izobola for Avena tatua chlortoluron: g.s.a /ha 0 200 300 ¦ 400 diflufenican: g.s.a /ha FIG. 3 600 6000 Gaiium aparine: ED 90 Izobola neburon g.s.a /ha 5000 i d i 1 iu fe n ican o. s. ? / ha FIG.4H8 016 Galium aparine: Izobola ED 90% tinuron (g.s.a/ha) 2C0 400 600 diflufenican (g.s.a/ha) FIG. 5 800 CONH-\7 V'F *N'' 0^ CF, PATTERN PL PL PL PL PL PL PL PL PL PL PL PL

Claims (1)

1.