WO2017078638A1

WO2017078638A1 - Synergistic herbicidal composition of oxadiazon and clomazone for use in rice

Info

Publication number: WO2017078638A1
Application number: PCT/TR2016/000156
Authority: WO
Inventors: Tuncay YILDIZTEKIN
Original assignee: Entovest Ilac Kimya Ve Teknoloji Arastirma Merkezi San TicLtdSti
Current assignee: Entovest Ilac Kimya Ve Teknoloji Arastirma Merkezi San TicLtdSti
Priority date: 2015-11-06
Filing date: 2016-11-07
Publication date: 2017-05-11
Anticipated expiration: 2018-05-06

Abstract

The present invention relates to new and synergistic combinations containing oxadiazon and clomazone molecules as active agents developed for ensuring an effective and broad-spectrum weed management through application prior to cultivating rice.

Description

SYNERGISTIC HERBICIDAL COMPOSITION OF OXADIAZON AND CLOMAZONE FOR USE IN RICE

The present invention relates to new and synergistic combinations containing oxadiazon and clomazone molecules as active substances developed for ensuring an effective and broad-spectrum weed management through application prior to cultivating rice.

FIELD OF THE INVENTION

Rice is the basic nutritional source for 40% of the world population and a staple food providing 80% of the caloric intake of approximately 2.7 billion people. Cultivated largely in tropical and temperate regions, 90% of rice is grown and consumed by Asian countries.

Rice is grown in five different cultivation systems in the world depending on the water regimen. These systems are irrigated rice, rain-fed lowland rice, deep-water rice, upland rice and coastal wetland rice considering the area of cultivation. In general, rice cultivation system is based on continuous irrigation; and rice is cultivated on waterlogged field in this system. The surface of the field is covered in water starting from planting until it is 20 days till the harvest. The height of water is increased gradually depending on the growth of the plant and kept around 15 cm during maximum growth stage.

Methods of planting used in irrigated rice cultivation system in the world vary depending on the economic, ecologic and social conditions of countries. Such methods are direct seeding in water (by broadcasting, fertilizer distributors and airplanes), drilling in dry land, hill planting and transplanting (by hand or drilling).

The biggest problem in the cultivation of rice, which is a significant staple food around the world, is the difficulty of controlling weeds. Weeds in paddy fields not only result in a great loss in yield but also cause producers to abandon the cultivated field. Furthermore, weeds host pests such as Scirpophaga incertulas Cnaphalocrocis medinalis. Since the labor to be exerted in the fields that are densely populated by weeds and the associated economic cost cannot be compensated from the rice harvested, such fields are either completely abandoned or the rice plants are plucked and other crops are planted. Planting a new crop is a process that takes place outside the ideal plantation season, thus, requiring higher labor and cost.

Before invention of herbicides, weeds in rice fields were removed manually. Experts in the agriculture industry were led to research the weed problem that could not be taken under full control due to inadequate workforce in such technique, difficulty of working in water-fed parcels, numerous health problems and particularly rheumatism resulting from working in such fields for a long term and other difficulties. As a result of such researches, herbicides were invented. The fact that paddy fields are in water-fed parcels result in increase in the weed population. The attack of dense population of weeds results in resistance to herbicides in a short time. Therefore, the search for herbicides with different action mechanism has always continued.

The underlying problem in weed management is that the herbicides used against the same group of weeds are applied continuously throughout years. Such non-rotation application, in combination with unchanging application method and unchanging application period, results in resistance to herbicides. Today, the weed problem in rice cultivation almost all around the world has come to a dead end due to resistance. Today, the global rice market and the rice as a staple food is under threat since new application methods and new herbicides cannot be developed. The present invention is intended to increase the effect derived from the synergy of the single combination of different herbicide molecules in order to eliminate such threat and manage greater number of weeds with a single application. STATE OF THE ART

In the prior art, FOB, Auxin hormones and herbicide active agents having ALS action mechanism and acting in contact were used in Turkey and many countries in the world. In many regions of the world, weeds have developed resistance to such herbicides, and resistant weeds such as Cyperus spp, Echinochloa spp and Alisma spp. can no longer be managed using such herbicides. Herbologists in various universities around the world still study on new means of solution or methods for the resistance management. However, neither a new molecule nor a new method has been developed until now. The unsolvable weed problem causes yield reduction by 35 to 70% in rice cultivation.

In the prior art, bensulfuron methyl, penoxsulam, bispyribac Na⁺ and other active agents from ALS group were used to manage Cyperus spp, Echinochloa spp, Digitaria sanguinalis (L.)Scop and Diplachne spp. Varying depending on the herbicides, the application period of such active agents is generally post-emergence when the rice has 2-3 to 6-8 leaves.

In the prior art mentioned above, the rice is submerged during that period, and the application is very difficult and expensive. Today, when the environmental effects of pesticides are understood more clearly, aerial applications are forbidden due to environmental awareness, and as a result, the solution to weed management problem has become more challenging. Wheeled tools are used in the field to apply herbicides to the submerged rice, which results in significant damages since such tools run over the plant culture. The present invention has eliminated such problems through a method of preplant herbicide application. In another prior art, cyhalofop butyl, fenoxaprop-P-ethyl from FOB group and other herbicide active agents having the same action mechanism were used to manage Cyperus spp, Echinochloa spp, Digitaria sanguinalis (L.)Scop and Diplachne fusca. The application period of such active agents is also post emergence when the rice has 4-8 leaves. Weeds develop resistance to the herbicides mentioned in the foregoing examples from the prior art after they are used for 5-7 years. The newest of such conventional herbicide molecules has been used for more than 20 years; therefore, the resistance problem has reached the maximum level due to long-term use. Such resistance of weeds has become a major problem in weed management in rice cultivation almost all around the world. Same applications for years have resulted in higher resistance of weeds, which cannot be prevented despite application of such herbicides in doses increased by 4-5 times. Today, it weed problem cannot be controlled due to such increased resistance.

In the prior art, weeds have developed high resistance to FOB, ALS, molecules acting in contact, Auxin hormones and other herbicide active agents acting in contact, and herbicide doses are increased due to such resistance. Such dose increase is possible for three commonly used (3) molecules, which do not cause phytotoxicity in rise. These are cyhalofob butyl, penoxulam and bentazon. Almost all the other molecules result in intolerable phytotoxicity in rice when applied in high doses. Therefore, it is not an alternative or option to increase the dose of molecules that result in phytotoxicity. In the prior art, increasing the dose of the abovementioned cyhalofob butyl, penoxulam and bentazon molecules from among the prior herbicide molecules is not a solution due to the high resistance. Effective weed management is not ensured despite a sevenfold increase in the dose of cyhalofob butyl and fivefold increase in the dose of penoxulam.

The fact that dose increase is not a solution in the prior art has led us to use a combination of such herbicides. Accordingly, cyhalofob butyl was combined with penoxulam (1) and bentazon was tried to be strengthened with MCPA. The results were the same with the prior art, and the resistance could not be eliminated. This is because weeds are resistant to both molecules used in the cyhalofob butyl + penoxulam combination, which fail to create a synergistic action on each other.

In the prior art, molecules having a new action mechanism other than the action mechanism mentioned above were researched; as a result, it was decided to use the herbicides containing oxadiazon and clomazone active agents separately through a new mode of action. The results were recorded at each location. All the results were parallel to each other, and the effect from separate use of these molecules was not at the desired level in weed management even though the results obtained were relatively better than that of the FOB, acetolactate synthase inhibitor (ALS), auxin hormones and herbicides acting in contact. Therefore, such molecules did not give a result suggesting they could be used alone as a means of solution. In such experiments, not only weed management but also effect on germination of rice (phytotoxicity) was assessed.

In the prior art, there was a resistance to FOB, auxin hormones, acetolactate synthase inhibitor (ALS) and herbicides acting in contact, and such herbicides are now removed from weed management programs for rice.

Oxadiazon is a Protoporphyrinogen oxidase (PPO) inhibitor, which also acts as a chlorophyll inhibitor. The chemical name of oxadiazon is 5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)- l,3,4-oxadiazol-2(3H)-one, and it is a molecule from Oxadiazole family. Oxadiazon is a highly persistent herbicide with a half-life of 3 to 6 months. This herbicide is strongly adsorbed on soil colloids, and it is not easily degradable. Oxadiazon is not considered to be volatile.

Conventional formulation types of oxadiazon (emulsifiable concentrate (EC), Water-soluble Powder (WP), Granule (G) and others) have been used in management of many weed species in cultivation of various crops aside from rice.

In the state of the art, oxadiazon has a limited use. As a result of the applications through this technique, Oxadiazon Emulsifiable Concentrate (EC) formulation caused great damage to the rice in cultivation areas where oxadiazon is used, and intolerable phytotoxicity was observed. In this technique, the soil was leached at least twice after application of oxadiazon in order to prevent phytotoxicity in rice, in spite of which the death of rice seeds was observed to be at an intolerable level.

In the prior art, oxadiazon was mostly used on lawns and in cultivation of onion, clove and many other agricultural products. Oxadiazon is an herbicide that rather has an effect on seeds. Conventional solid or liquid formulations that contain oxadiazon have been used in rice cultivation, even if not commonly. However, a balance could not be established between the effective dose and phytotoxicity in applications where oxadiazon molecule is used alone. Oxadiazon doses over 25 g a.i/da prevent germination in rice whereas doses < 25 g a.i/da result in tolerable phytotoxicity in rise. Even though such dose is tolerable in terms of phytotoxicity, it is extremely unsuccessful in terms of weed management. Therefore, rice farmers cannot use the products that contain oxadiazon unless they are completely out of solutions.

Furthermore, even though oxadiazon molecule is considered independently from phytotoxicity in rice, it is only effective on weeds Echinochloa crus-galli, Cyperus difformis and Alisma plantago- aquatica, for which the effective dose of oxadiazon is > 35 g a.i/da, which results in intolerable phytotoxicity in rice. Due to such phytotoxicity, it is not always possible to apply the effective dose, and oxadiazon is not effective on other weeds that pose a serious problem in paddy fields. The most significant example is Echinochloa oryzoides, a species of weed on which oxadiazon has not sufficient effect. Oxadiazon is mostly effective on a couple of broad-leaved weeds whereas it has no effect on narrow-leaved weeds in terms of weed management.

In the prior art, planting of the rice seeds was tried to be postponed for a long time after at least 2 leaching processes performed after oxadiazon was applied; however, this could not prevent growth of weeds. While climatic conditions are not always favorable for postponing the planting process, it was also recorded in the test results that the effective dose of oxadiazon was lost since it was exposed to direct sunlight in the soil. Effective dose significantly drops as a result of both the leaching process and conditioning and then fails to manage the growth of weeds.

In the prior art, the starting dose was increased in order to prevent the amount of oxadiazon, which was lost due to leaching and conditioning, from dropping below the effective dose, and this resulted in economic loss and unnecessary ecologic pollutions.

In the prior art where oxadiazon was applied, high starting doses resulted in chemical pollution of non-target areas when the soil was leached. In particular, release of petroleum-derivative solvents and emulsifiers found in the EC formulation (emulsifiable concentrate) to the nature resulted in ecologic pollution. It was mentioned above that, in the prior art, it was necessary to perform the leaching process at least twice in case of using Oxadiazon. In areas where there is water shortage, the water required for the leaching process cannot be procured; in that case, either rice cultivation is abandoned or other solutions are sought.

In the prior art, high starting doses may prevent germination of rice. When leaching and conditioning processes are not performed using the correct techniques, high doses of oxadiazon will remain the soil and cause germination of the rice stop completely.

In case of using Oxadiazon as in the prior art, even though the leaching is performed correctly, herbicides accumulate in certain parts of fields and such parts give no rice yield.

In another prior art, the leaching is performed generally after 4 days of applying the herbicide and the planting is performed after conditioning for 6 days. In the prior art, the oxadiazon in soil reduces or completely depletes due to leaching during the conditioning after day 4 or later. This results in germination of new weed seeds in the period of 6 days. In addition, only the weed seeds to germinate in the beginning are managed and the weed seeds to emerge later cannot be controlled. In other words, the effect does not last long.

In the prior art, it is needed to use other herbicides as well in management of several species of weeds since the spectrum of oxadiazon molecule is narrow aside from its other adverse effects.

Clomazone is a carotenoid biosynthesis inhibition (unknown target), an herbicide that acts by inhibiting chlorophyll, and its chemical name is 2-[2-chlorophenyl)methyl]-4,4-dimethyl-3- isoxazolidinone. It is from the isoxazolidinone family.

Clomazone molecule has completely no effect on Cyperus spp, Alisma spp.. Even though it is more effective than oxadiazon on Echinochloa oryzoides, the effectiveness on such weed ends within a short time. Its effect on Echinochloa crus-galli lasts for less than 30 days. Clomazone has never been a solution in rice when used alone. This molecule has a limited use as a part of a program. Clomazone is mostly used in cultivation of soya, canola, tobacco and other agricultural products.

Another prior art is related to use of clomazone molecule. Clomazone is not an effective molecule in weed management when used alone and there are only a few weed species controlled by this molecule.

In the prior art, clomazone application was tried in two separate techniques. The first technique involves application when rice has 2-3 leaves. In this period, it is desired to use iron-wheeled tractors to apply to herbicide, which significantly damages the rice.

When clomazone is applied after rice is planted, it is not possible to manage the weed seedlings that germinate prior to planting rice since clomazone is effective on seeds.

In the prior art, the second application technique involves application prior to cultivation. The dose is doubled in this application technique, and such dose increase damages the rice.

In the application technique of clomazone in the prior art, it was tried to apply clomazone in higher doses for management of certain weeds on which clomazone had insufficient effect. However, desired results were not obtained and whitening and irreversible phytotoxicity were observed in rice.

In the prior application technique of clomazone, high phytotoxicity is observed in rice species other than Osmancik rice.

Clomazone is used alone at 75 g a.i/da dose, which causes severe phytotoxicity and death of rice particularly in sandy soils. Due to such results, use of clomazone molecule is kept to a minimum.

Clomazone is effective only on certain narrow-leaved weeds and not effective on some of the narrow-leaved and broad-leaved weeds. Since clomazone has a narrow spectrum, it has always been necessary to use different herbicides, as well.

OBJECTS OF THE INVENTION

In consideration of the prior art described above, it appears that it is not possible perform effective weed management in rice by using the conventional herbicides. Based upon the strengths of oxadiazon and clomazone molecules, the inventors have aimed to strengthen the weaknesses of these molecules through synergy and discovered that these two molecules within the same combination have a synergy on each other. Thus, the inventors have developed an herbicide that offers a longer management duration, a greater effect and effect on greater number of weeds (broad- spectrum).

The inventors aim to ensure management of weeds that are resistant to FOB, acetolactate synthase inhibitor (ALS), Auxin hormones and herbicides acting in contact using the invention.

With the present invention, the inventors have also succeeded at managing certain weeds (Echinochloa oryzoides, red rice) that are unmanageable when the two molecules are used separately.

The inventors have broadened the narrow spectrums of oxadiazon and clomazone molecules with a dual chlorophyll blockage obtained from the combination in addition to the synergistic effect.

The inventors also aim to eliminate all narrow and broad leaved weeds in rice prior to germination of rice. The inventors have intended to eliminate the antagonism problem (elimination of the effect of one molecule by the other) happening in the mixture obtained by putting these two molecules in separate tanks at the disinfestation process, and eliminated such problem though the emulsifiers and solvents used in the formulations. This invention is also included in the scope of the existing application. The inventors have aimed to develop an herbicide that is effective at lower doses without damaging the rice by means of benefiting from the synergy of different molecules for weed management in a safe way in case of rice species that are sensitive to herbicides.

The inventors have also aimed to ensure economy by developing an herbicide formulation that may also be effective at lower doses and minimize environmental pollution by minimizing use of chemicals. The inventors have aimed to solve the unsolved weed management problem resulting from resistance by combining certain herbicides from different groups that have the same action mechanism but are effective in different ways.

The inventors have aimed to break the resistance by means of applying chlorophyll inhibitor by benefiting from the same action mechanism of the two herbicides and applying the two herbicides separately on the same area. Oxadiazon as Protoporphyrinogen oxidase inhibition (PPO) and clomazone as carotenoid biosynthesis inhibition play a role in prevention of chlorophyll formation. Such prevention of chlorophyll formation through these two methods provides a powerful effect on resistance, and the inventors have intended to ensure full management of weeds in areas where resistance is seen.

When clomazone and oxadiazon molecules are used individually, it is not possible to manage Echinochloa oryzoides, Echinochloa sp. (Early barnyard grass. Species has yet to be identified) and red rice. Through use of a combination of oxadiazon and clomazone, the inventors have aimed to manage such weed species which are impossible to manage with conventional herbicides of the prior art.

The inventors have also discovered during the invention that the synergistic action is higher when pendimethalin herbicide molecule is added into the clomazone + oxadiazon combination. Such combination has contributed in management of certain weed species, allowing the inventors to broaden the spectrum and increase the effectiveness. The inventors have also aimed to manage the weeds in the spectrum of both individual molecules at higher levels and permanently through the invention.

In a sense, the inventors have aimed to minimize phytotoxicity in rice by weakening the strong adsorption characteristic of oxadiazon molecule through use of clomazone and decreasing the entrainment rate of clomazone with water by using oxadiazon in order to increase effectiveness in weed management.

The inventors have also aimed to develop a formula that eliminates the disadvantages of the herbicides used in weed management in rice cultivation. In this sense, the inventors aim to develop a product that provides effective weed management and saves on the environment, productivity, costs and workforce by means of developing a formula for use of the combination oxadiazon and clomazone active substances, which has caused no resistance problem yet but are unable to give the desired result when used individually, prior to planting rice and controlling the weeds when they are seeds. The inventors also intend to develop an environmentally safe product by preventing use of generally petroleum-based solvents and emulsifiers that are released from rice parcels into underground and surface waters.

By using the oxadiazon and clomazone combination that is explained in detail below, the inventors have aimed to manage all weed species that pose a problem in rice cultivation through a single application and increase the yield in rice cultivation areas with an intention of not causing any damage to rice seeds during application.

The inventors have aimed to develop a more economical and more ecologic new herbicide by decreasing the effective doses of oxadiazon and clomazone molecules when they are used separately through the synergy of the molecules in the combination subject to the invention. The inventors have achieved the targeted objective, and the individual effective doses of each molecule were dropped by more than 30%.

The inventors have aimed to ensure effective weed management by lowering the effective doses and solve the problem by applying lower amount of chemicals to the environment. It is another intention of the inventors to solve the weed management problem that individual oxadiazon and clomazone molecules are unable to solve through the synergy derived from the optimum combination of these two molecules.

The inventors have intended to decrease the number of disinfestation from 6 to 8 times to once in a season through the invention. The season of application of the invention is pre-cultivation, which is observed to be the easiest and the ideal period to apply the herbicide. The invention has eliminated all the narrow- and broad-leaved weed species located in the field with a single application prior to cultivation. As a result, it was observed that it is a new invention for management of all weed species with a single application prior to cultivation and without entering the cultivated field.

During the studies conducted regarding the existing problems in the prior art and the objectives given above, the inventors have found out that the combined use of oxadiazon and clomazone molecules serves as a surprisingly effective method in prevention of weed emergence providing an effective weed management by causing minimum phytotoxicity in rice seeds and that these two molecules have a surprisingly synergistic action.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to formulation of clomazone and oxadiazon molecules together as a single combination, which are known in the agricultural industry for their weed management effects in rice cultivation areas but unable to manage resistant weeds at the desired level. The invention has eliminated the unsolved weed problem in rice cultivation when these two molecules are used as a combination. Furthermore, these two molecules can be effective on the same weed species while each of the molecules can be effective on different weed species.

Individual use of the two molecules manages only a few number of weed species. With the present invention, the weed species on which these two molecules have a joint effect have been managed at a higher level and for a longer duration, and the weed species on which the two molecules have no effect when they are used individually have been managed with a single application thanks to the synergy created.

With the present invention, the weed species on which clomazone and oxadiazon have a joint effect can be managed at a higher level and for a longer duration thanks to the synergy of such molecules.

On the other hand, it was discovered that the weed species on which clomazone is effective and oxadiazon has no or insufficient effect or oxadiazon is effective and clomazone has no or insufficient effect could be managed at a higher level and for a longer duration by means of the synergy obtained from the use of the subject molecules within a single combination.

In other words, not only the number of weed species managed by formulating a single combination of such molecules has been increased but also the level of effect and effective duration have been increased (Table 1). Such advantage of the invention has added a new dimension to the solution of weed problem in rice, and the formula developed has been a strong means of solution.

The invention is an effective combination that does not damage the rice since it is applied through easy labor and at economical costs in a single dose prior to cultivation and without needing any other herbicide during the time until the harvest.

The studies, the results of which are given in the table below, were conducted at 19 Mayis University, Faculty of Agriculture, Plant Protection Department and company specialists.

2. Echinochloa oryzoides 45-65 <10 60-90 ; <15 j >95 i >52

3. Cyperus spp. j 90-92 <30 ^■ 1-3 - >96 ^:≥25

4. Alisma spp. j 93-96 ^: >30 0 ! - ! 93-96 >30

5. Digitaria spp. j 5-10 <7 ; 90-93 >45 ; >95 >53

6. Lindernia spp. 14-17 ! <10 90-92 1 >45 \ >97 i >60

7. Diplachne (leptochloa) ; 5-10 \ <15 93-94 <50 >98 !≥≤2 spp.

8. Red rice Ϊ 10-12 j <8 ! 40-50 <20 ί >90 ; >3o j

9. Panicum spp. 90-92 ; >25 5-7 - >95 >45

10. Echinochloa sp. (Early 5-10 ; - j 25-30 ! <i o ! %90 I |>30 barnyard grass - A new

species yet to be

identified in Turkey)

1) Even though both products are effective on the weed species number 1, the effect level increases and the effect duration is longer at a lower dose of the combination subject to the invention. The results are positive in terms of synergy.

2) The molecule (A) has no effect and the molecule (B) passes the limit value of 90% at a high dose in the weed species number 2. Surprising level and duration of effect were obtained with the invention.

3) The molecule (A) is found to be effective whereas the molecule (B) has no effect in the weed species number 3. The invention shows great synergy as in the case of the weed species number 3, and the effectiveness was increased and the duration effect was extended with the invention. 4) No synergy is seen in the weed species number 4; however, since other weed species are managed through the applications to be made for this weed species, the invention is especially beneficial since it is easy to use in the industry and provides management of more than one species of weed at a single time.

5) Whereas molecule (A) is not effective on the weed species number 5, the molecule (B) is effective at a limit value. Again, the effectiveness of the invention increases extraordinarily and the effectiveness is observed to last longer at a lower dose (¾ of the normal dose).the synergy of the two molecules obtained from the invention is also clearly observed in this species of weed. 6) The synergy is seen in the weed species number 6 and 7 as in the case of the weed species number 5.

7) The weed species number 8 is a weed that has great similarities to rice. Therefore, its management in paddy fields is not easy. Whereas the molecules (A) ad (B) have no effect on this weed species when they are used individually, it is observed that the invention that is formulated by the combination of these two molecules effectively manages such unsolvable weed problem.

8) Whereas the molecule (A) is effective at a limit value on the weed species number 9, the effect of the molecule (B) is not sufficient. The synergy obtained from the invention maximizes the effect and the effective duration in management of this weed species.

9) The weed species number 10 is species of weed, which has been the most challenging weed in terms of management in the recent years. Its species is not fully identified yet. Even though the molecules (A) and (B) are not effective on this species when they are used individually, the combination obtained in the invention has surprising level of effect on the species. In the present invention, the strengths of these two molecules have been used to strengthen their weaknesses, and an ideal formula has been developed for effective weed management.

The present invention has a broad spectrum, managing all narrow- and broad-leaved weed species such as Echinochloa crus-galli, Cyperus spp., Echinochloa oryzoides, Alisma spp., Digitaria spp., Lindernia spp., Diplachne (leptochloa) spp. red rice, Panicum spp. Echinochloa sp. (Early barnyard grass. A new species yet to be identified in Turkey).

The combination of oxadiazon and clomazone molecules subject to the present invention eliminates the need for another herbicide since they are effective on a broad spectrum of weeds thanks to their synergistic action. The synergistic action of the combination of oxadiazon and clomazone molecules subject to the present invention has an effect on a broad spectrum, thus eliminating the need for another herbicide.

Another objective of the invention is related to a method of application on the soil prior to cultivation, which aims to develop an easier disinfestation program.

The present invention relates to a method of application of a combination of oxadiazon and clomazone molecules in order to eliminate the weeds in paddy fields. The subject method comprises the following steps:

(i) Application of the oxadiazon + clomazone combination on the field to be cultivated right after harrowing the soil prior to planting rice, (ii) Irrigation of the field to be cultivated within minimum one day and preferably 4 days from application of the invention,

(iii) Spreading seeds within minimum one (1) day, preferably four (4) days and most preferably six (6) days from irrigation of the cultivation field. Below given are certain basic considerations related to the application of the method subject to the invention:

1) The soil is harrowed, the success of the invention extraordinarily increases on harrowed soil.

2) The invention should be applied on the soil right after it is harrowed without conditioning.

3) The invention is pulverized onto the surface of the soil using t-jet nozzles to apply the recommended dose.

4) The invention is used with 30-40 liters of water per decare. The device should be calibrated for adjusting the dose.

5) The soil should never be conditioned after the invention is applied.

6) The soil should be irrigated within minimum one (1) day and preferably four (4) days from application of the invention; the seeds should be spread within at least one (1) day, preferably four (4) days and most preferably (6) days from releasing water to the field.

7) Drying periods should not be kept long in order to ensure the invention shows full performance.

8) Over-drying should be avoided and the surface of the soil should not crack.

In the subject method, rice seeds are placed in a container filled with water to break the seed coats. Such container may be a sack, wooden box or a plastic container. It is not necessary to break the seed coats.

In the method explained above, oxadiazon active substance from among the active substances in the invented combination may be applied at a dose between 3.5 g a.i/da and 210 g a.i/da and preferably between 17.5 g a.i/da and 70 g a.i/da on the field. Such doses are 30% less than the individual application doses of oxadiazon in the prior art, proving that the effectiveness of the invention increases depending on the synergy.

In the method explained above, clomazone active substance in the invented combination is applied at a dose between 3.5 g a.i/da and 280 g a.i/da and preferably between 15 g a.i/da and 95 g a.i/da on the field. The doses range because of the changes resulting from the soil type, weed density and level of resistance, climatologic conditions, species or type of weed and other factors that will affect the effectiveness. Other effective doses to be tested and found depending on the local conditions are also included within the scope. The inventors have observed as a result of their studies that the above application method of the invention has unexpectedly increased the effectiveness, and thus, a new method has been developed along with a cost-efficient, effective and easy-to-apply formulation in weed management in paddy fields. Therefore, the present invention relates to a combination of oxadiazon + clomazone where the inventors benefit from the synergistic action of the molecules for application of the combination on paddy fields and a method developed for such combination, comprising the following steps:

1. Application of the formulation obtained from the combination of oxadiazon and clomazone on the soil prior to transplanting the rice seeds,

2. Irrigation of the area to be cultivated at least 24 hours after applying the formulation, 3. Soaking the rice seeds put in sacks in water at least 48 hours before applying the formulation and transplanting the germinating rice seeds (popped or cracked) to the prepared area.

The term "germinating" used within the scope of the present invention also stands for popped or cracked seeds. In application of the method, it is preferred to soak the seeds; however, any cultivation without performing the germination is included within the scope of the method of application of the invention.

During the studies conducted, the inventors have observed that the seeds of all narrow- and broad- leaved weeds on the field lost their germination strength by or over 95%, for example by 96%, 97%, 98%, 99% or %100, upon application of the combination subject to the invention onto the cultivation field prepared and a surprisingly high effectiveness was obtained in weed management. In this application, the individual application doses of each molecule were further decreased by minimum 30%. In the applications performed, the paddy field was irrigated within at least 24 hours and preferably 96 hours from the application; and the rice seeds ready to germinate were broadcasted onto the surface of the water within preferably 114 hours from such process. Thus, the rice seeds that were soaked in sacks or another suitable container were not affected by the formulation comprising the combination of the two molecules. Therefore, this method, which is very safe for rice, provides high effectiveness in weed management.

In the method to be applied within the frame of the present invention, the composition that contains oxadiazon + clomazone subject to the invention can be used alone. On the other hand, at least one different active agent can be used in addition to the oxadiazon + clomazone active agent within the scope of the present invention. Such other active agent can be mixed in a tank together with the oxadiazon + clomazone composition at the time of application or at another stage of the production of the composition by addition or applied from a different tank at the time of applying the oxadiazon and clomazone combination subject to the invention. Subject additional active agent or agents may be one or more molecules or a combination of molecules selected from the group of HRAC (Herbicide Resistance Action Committee) WSSA (weed science society of America) Group: 5, 6, 7, 9, 10, 11, 12, 13, 14, 15 or benzobicyclon, butachlor, oxadiargyl, pretilachlor, thiobencarb, pentrazamide, quinclorac, paraquat, diquat, quinmerac, Oxyflourfen, amitrole, aclonifen, acifluorfen-Na, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, azafenidin, carfentrazone- ethyl, sulfentrazone, pyraclonil, profluazol, flufenpyr-ethyl, benzfendizone, butafenacil, pentoxazone, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, cinidon-ethyl, flumioxazin, flumiclorac- pentyl, beflubutamid, fluridone, flurochloridone, flurtamone, benzofenap, pyrazolynate, pyrazoxyfen, isoxachlortole, isoxaflutole, fluthiacet-methyl, thidiazimin, norflurazon, glufosinat, mesotrione, tembotrione, topramezone, isoxaflutole, fenklorin, pendimetalin, fenoksaprop, ethoxysulfuron, metsulfuron, klorimuron, safener, azimsulfuron, metsulfuron methyl, chlorimuron ethyl, oxaziclomefone, norflurazon, clomazone and isoxaflutole. Furthermore, the present invention relates to elimination of severe phytotoxicity seen in rice when the two molecules are applied individually. Elimination of phytotoxicity is, in a sense, related to selection of the inactive agents used in the invention from a safe group and development of safe formulations.

In general, the invention relates to formulation of oxadiazon and clomazone molecules together. The invention may comprise oxadiazon and clomazone in the same formulation types or together with different formulation types. In other words, oxadiazon and clomazone may either be formulated together in a single type of formulation or be brought together after they are prepared in different formulation types. If prepared in different formulation types, these formulations may be applied separately or simultaneously or consecutively or at different times. The invention may be a single formulation that contains the same formulation of each molecule comprising the combination or a multiple formulation that contains different formulations of each molecule comprising the combination.

An example to the single formulation of the invention: The formulation of the invention will be Emulsifiable Concentrate (EC) if both Oxadiazone and Clomazone are in Emulsifiable Concentrate (EC) form.

The single formulation type of the invention will be one from Emulsifiable concentrate (EC) oil-in- water or water-in-oil emulsion (EW), suspension concentrate (SC), micro-emulsion concentrate

(MC), capsule suspension or microencapsulation (CS), oil-based concentrate (OD, ODC), solutions

(SL) and all of the other conventional liquid formulations, water dispersible granule (WDG, WG), soluble granule (SG), wettable powder (WP), dust (D), granule (G), effervescent granule (E. Gr), tablet (Tb), water soluble package (WSP) and all of the other conventional solid formulations.

The single formulation type preferred for the invention will be capsule suspension (CS). However, the formulation of the invention may include without limitation all of the other single formulation types mentioned above / existing in the state of the art.

An example to the multiple formulation of the invention: The formulation of the invention will be ZE when Oxadiazon is in Capsule Suspension (CS) form and Clomazone is in Emulsifiable Concentrate (EC) form.

The multiple formulation type of the invention may be one from ZC (CS and SC), ZE (CS and EC or CS and SE), ZW (CS and EW), SE (SC and EC or SC and EW) and all the other multiple (multicharacter) formulations.

If the invention is in multiple formulation type, any of the molecules in the combination may be any of the single formulations. In other words, the single formulations mentioned above will be individually used as oxadiazon or clomazone formulation type. In multiple formulations, it is sufficient to include different formulation types of different molecules in the same combinations.

The formulation type preferred in the invention will be ZE. However, the formulation of the invention may include without limitation all of the other multiple formulation types mentioned above / existing in the state of the art.

In the formulation subject to the invention, the ratio of molecules will be 4.8 units of Clomazone and 0.12 to 6.0 units of oxadiazon. The preferred range or ratio is 4.8 units of clomazone and 2 units of oxadiazon. Accordingly, when 4.8 units of clomazone used, the unit of oxadiazon to be used can be 0.12, 0.16, 0.18, 0.20, 0.22, 0.24, 0.30, 0.35, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8 or 6.0 or any other unit within the range defined. The invention can be formulated with not only the preferred ratio but also 4.8 units of clomazone and 0.12 to 6.0 units of oxadiazon as indicated above without limitation any limitation.

The units of oxadiazon range because of the variables such as the soil type, climatological conditions, weed species, weed density and resistance.

Such ratios have been discovered as the problem-free ratios in terms of effectiveness and phytotoxicity within the scope of the invention. The % values given in the table below can be formulated based on such ratios.

Table 1. General and preferred ratios of the components that constitute the invention Component General % (by Preferred % (by

weight) Content weight) Content

Oxadiazon 0.0010 - 60 20

Clomazone 0.0024- 96 48

Emulsifier mix 0.001-35 0.1-26

Solvent 1-60 5-34

Antimicrobial preservative 0.0001-59 0.1-27

Antifoam 0.001-60 0.1-32

Antifreeze 0.01-60 0.1-28

Reactant 1 0.001-70 0.20-25

Reactant 2 0.001-60 0.21-28

Reactant 3 0.001-70 0.15-19

Stabilizer 0.0001-30 0.02-12

Carrier Takes up to 100% Takes up to 100%

Production of the formulation example with given percentages:

• Preparation of an emulsifiable Oxadiazon solution by mixing oxadiazon, solvent, antioxidant preservative and the capsule reactant 1, · Preparation of the water phase of the emulsion by adding the emulsifier mix, antifreeze, antimicrobial preservative and antifoam into water,

• Emulsification of the oxadiazon solution in water phase with the help of high-speed mixer,

• Slow addition of the other reactants, which are the reactant 2 and the reactant 3, into the emulsion prepared, and · Conditioning of the mixture to finalize the polymerization reaction initiated and then adjusting the viscosity with the help of the stabilizer.

In the formulation according to the present invention, the amount of oxadiazon used is 0.001-60%, preferably 5-50%, most preferably 10-45%) by weight. In the formulation according to the present invention, the amount of clomazone used is 0.0024- 96%, preferably 0.5-70%), most preferably 1-60% by weight.

Other chlorophyll inhibitor or photosynthesis inhibitor herbicides in addition to WSSA Group: 5, 6, 1, 9, 10, 1 1, 12, 13, 14, 15 are included within the scope of the invention, and one or more selected therefrom can be used as an alternative to either one of oxadiazon or clomazone. Furthermore, one molecule or a combination of more molecules selected from among benzobicyclon, butachlor, oxadiargyl, pretilachlor, thiobcncarb, pcntrazamidc, quinclorac, paraquat, diquat, quinmcrac, Oxyflourfen, amitrole, aclonifen, acifluorfen-Na, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, azafenidin, carfentrazone-ethyl, sulfentrazone, pyraclonil, profluazol, flufenpyr-ethyl, benzfendizone, butafenacil, pentoxazone, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, beflubutamid, fluridone, flurochloridone, flurtamone, benzofenap, pyrazolynate, pyrazoxyfen, isoxachlortole, isoxaflutole, fluthiacet-methyl, thidiazimin, norflurazon, glufosinat, mesotrione, tembotrione, topramezone, isoxaflutole, fenklorin, pendimetalin, fenoksaprop, ethoxysulfuron, metsulfuron, klorimuron, safener, azimsulfuron, metsulfuron methyl, chlorimuron ethyl, oxaziclomefone, norflurazon, clomazone and isoxaflutole can be used as an alternative to either one of oxadiazon or clomazone.

The amount of such molecules used can be 0.001-60%) by weight and 0.0024-96%) by weight when they are used as an alternative to oxadiazon and clomazone, respectively. Use of one or more of such alternative molecules as an addition to the clomazone and oxadiazon composition (the invention) is included within the scope of the invention. In case of an addition of molecule to the invention, the total amount of additional molecule or molecules used shall be 0.001-72%) by weight.

The emulsifier mix mentioned in the table may be either combination of multiple emulsifiers or an individual emulsifier. Such emulsifiers may be from ionic, anionic and nonionic groups or a combination of such groups. The emulsifier that can be used in the product may be one or a combination by different ratios of more selected from the group of amine ethoxylates, EO/PO block polymers, ether sulfates, saturated alcohol alkoxylates, saturated alcohol ethoxylates, sorbitan ester ethoxylates, tributylphenol ethoxylates, phosphate esters, tristyrylphenol ethoxylates, sulfonation products, polycondensation products, nonylphenol ethoxylates, alkyl benzene sulfonates, castor oil ethoxylates, EO/PO alkoxylation products, saturated alcohol ethoxylates, olein sulfonates and sulfosuccinate. Preferred emulsifiers used in the formulation are tristyrylphenol ethoxylates and nonylphenol ethoxylates. When the combination of tristyrylphenol ethoxylates and nonylphenol ethoxylates are used in the emulsifier mix, the preferred ratio of the emulsifier mix is 1 : 1 by weight. In the formulation according to the present invention, the amount of emulsifier mix used is 0.001- 35%, preferably 0.01-30% and most preferably 0.1-26% by weight.

The solvent mentioned in the Table is the liquid medium in which the Oxadiazon active agent, which is in a solid state under normal conditions, is solved. Since the invention is performed with interfacial surface polymerization, it can only be formulated using non-water-soluble solvents. For such purposes, hydrocarbons such as xylene, benzene, toluene, cyclohexane, solvesso 100, solvesso 150, solvesso 200 and exxsol series in addition to herbal oils derived from oily seeds and ethyl and methyl esters thereof and herbal terpenes are also included within the scope of the patent. A combination of more than one solvent can be used instead of a single solvent. The preferred solvent used in the formulation is xylene in the amount less than that of the conventional technical formulations.

In the formulation according to the present invention, the amount of solvent used is 1-60%, preferably 3-50% and most preferably 5-34% by weight.

The antimicrobial preservative mentioned in the Table is butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).

In the formulation according to the present invention, the amount of antimicrobial preservative used is 0.0001-59%, preferably 0.005-50% and most preferably 0.1-27% by weight.

The antifreeze indicated in the table is glycol derivative additives known in water-based pesticide formulations for their antifreeze properties at low temperatures. Such additives are ethylene glycol, monopropylene glycol, dipropylene glycol, diethylene glycol and glycerin. The preferred additive used in the formulation is monopropylene glycol.

In the formulation according to the present invention, the amount of antifoam used is 0.001-60%, preferably 0.05-50% and most preferably 0.1-32% by weight.

The reactant 1 indicated in Table is organic compounds containing isocyanate functional group. The function of the reactant 1 in the formulation is to create a polyuria capsule wall upon being polymerized in the emulsion droplets-water interface with the help of catalyzer solution after emulsification of the Oxadiazon prepared with the oil phase. The reactant 1 may be methyl isocyanate, methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexyl isocyanate (HMDI) or isoprene diisocyanate (IPDI).

In the formulation according to the present invention, the amount of the Reactant 1 used is 0.001- 70%, preferably 0.05-50% and most preferably 0.02-25% by weight. The reactant 2 and reactant 3 indicated in the Table are amines that create a polyuria capsule shell after they enter into polymerization reaction with the reactant 1 that is the isocyanate group. The reactant 2 and reactant 3 are premixed together in water to prepare the catalyzer solution. The catalyzer solution prepared is slowly added onto the Oxadiazon oil base emulsified in water to start the reaction to create the polyuria capsule shell. The amines used in the synthesis of the polyuria capsule shell may be from primary, secondary or tertiary amine groups. The said reactant 2 and reactant 3 includes ethylamine, ethylene diamine, diethylene triamine, triethylene tetramine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine . In the formulation according to the present invention, the amount of the Reactant 2 used is 0.001- 60%, preferably 0.05-50% and most preferably 0.21-28% by weight.

In the formulation according to the present invention, the amount of the Reactant 3 used is 0.001- 70%, preferably 0.05-50% and most preferably 0.15-19% by weight.

The stabilizer indicated in the Table is the additives that may be used to adjust the viscosity of the formulation after the polymerization reaction ends. These include xanthan gum, guar gum, gum Arabic, carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose. The preferred stabilizer used in the formulation is xanthan gum.

In the formulation according to the present invention, the amount of the stabilizer used is 0.0001- 30%, preferably 0.05-20% and most preferably 0.02-12% by weight. In the formulation according to the present invention, the carrier is used in the amount that will take up the formulation to 100% by weight.

Based on the formulation type of the invention, different production methods may be used within the techniques known and the amounts of the components may be changed.

The preferred carrier indicated in the table is water. Antifoam and antimicrobial preservative are the additives that are commonly used in pesticide formulations. The preferred antifoam used in the formulation is silicone-based antifoam.

The composition of the invention indicated in the Table above is only given for one of the combinations included in the scope of the invention. Production of different ratios (% content) and different formulations using all familiar production techniques is included in the scope of the invention without any limitation.

In a sense, the invention is intended for using the molecules in lower doses than that of their individual uses due to their synergistic action. The invention is the combination of oxadiazon and clomazone, and such two molecules are used within a single combination. A powerful synergistic action was obtained from such discovery, and weed management was accomplished at a lower dose than individual use of the two molecules. This has allowed for using lower doses than the effective doses of the two molecules when they are used individually, and the new doses derived from the synergy have not caused phytotoxicity in rice. While lower dose is sufficient for weed management, corresponding to an amount of herbicide that is within the safe limits for rice.

With the present invention, effectiveness has been provided in weed management at a dose 30% lower than the normal dose of oxadiazon and clomazone, and no phytotoxicity has been observed in rice plant. In other words, thanks to the synergistic action from use of clomazone and oxadiazon molecules together, an effective disinfestation is obtained by using lower doses as active agent and formation of any phytotoxicity in rice plant is prevented.

When oxadiazon molecule is used individually at dose 30-100 g a.i/da and clomazone molecule is used individually at dose 45-150 g a.i/da, they are effective allowing for weed management in their spectrum. The doses range due to weed type, soil structure and climatologic conditions. Even though such doses of both molecules are effective on certain weed species, they have a limited use since they cause phytotoxicity higher than the damage threshold in rice. The present invention lowers the doses of these molecules separately thanks to their synergy, resulting in no phytotoxicity in rice. In the combination subject to the invention, the doses are lowered by minimum 30% for both molecules. >92% success has been obtained in weed management at such lower doses thanks to the synergy. Furthermore, the phytotoxicity in rice has been eliminated as a result of the lowered doses.

Clomazone molecule that moves fast in sandy soil causes severe phytotoxicity in rice.

On the other hand, oxadiazon molecule is strongly adsorbed on all kinds of soil with a persistence of minimum 3-6 months in soil.

The present invention has decreased the downward vertical movement rate of clomazone molecule in soil. Clomazone stays on the desired layer of the soil thanks to its binding to oxadiazon, which is strongly adsorbed on soil colloids.

The invention decreases the downward vertical movement rate of clomazone and balances the persistency of oxadiazon on the surface of soil by minimizing it. In other words, joint use of oxadiazon that is horizontally adsorbed on soil longer than desired and clomazone that has a vertical movement rate faster than desired has brought a balance; thus, the invention both eliminates phytotoxicity and provides effective weed management by maintaining the effective dose in the target area.

The balanced maintenance of the invention in the target area is achieved by the combination of the two molecules, which has brought an effective solution to weed management particularly in sandy soils.

In the formulation subject to the invention, the ratio of molecules will be 4.8 units of Clomazone and 0.12 to 6.0 units of oxadiazon. The preferred range or ratio is 4.8 units of clomazone and + 2 units of oxadiazon (E.g. 48% clomazone + 20% oxadiazon).

Given ratios are for general applications. The ratios may change depending on the field, geographical conditions, climatological differences, weed species and densities. The invention has ensured obtaining a high synergy for the effectiveness of oxadiazon and clomazone with such ratios at lower doses.

The present invention has been designed to eliminate the antagonism in tank mixtures of these two molecules. Coating of both molecules with special adjuvants and polymer coats has prevented molecules from interacting.

Claims

1. An herbicide composition for use in weed management, characterized in that clomazone and oxadiazon are formulated in a single combination.

2. A composition according to Claim 1, characterized in that the said oxadiazon and clomazone molecules are formulated together.

3. A formulation according to Claim 2, characterized in that the said oxadiazon and clomazone molecules are prepared in separate formulation types and brought together.

4. A formulation according to Claim 3, characterized in that the said formulation is in ZC form, wherein either one of clomazone or oxadiazon is formulated in CS form while the other in SC form.

5. A formulation according to Claim 3, characterized in that the said formulation is in ZE form, wherein either one of clomazone or oxadiazon is formulated in CS form while the other in EC form or in CS form while the other in SE form.

6. A formulation according to Claim 3, characterized in that the said formulation is in ZW form, wherein either one of clomazone or oxadiazon is formulated in CS form while the other in EW form.

7. A formulation according to Claim 3, characterized in that the said formulation is in SE form, wherein either one of clomazone or oxadiazon is formulated in SC form while the other in EC form or in SC form while the other in EW form.

8. A formulation according to Claim 3, characterized in that either one of oxadiazon and clomazone is in form of emulsifiable concentrate (EC) oil-in-water or water-in-oil emulsion (EW), suspension concentrate (SC), micro-emulsion concentrate (ME), capsule suspension or microencapsulation (CS), oil-based concentrate (OD, ODC), solutions (SL) and all of the other conventional liquid formulations, water dispersible granule (WDG, WG), soluble granule (SG), wettable powder (WP), dust (D), granule (G), effervescent granule (E. Gr), tablet (Tb), water soluble package (WSP) and all of the other conventional solid formulations, wherein oxadiazon and clomazone are in different forms.

9. A formulation according to Claim 2, characterized in that the said oxadiazon and clomazone molecules are prepared in the same formulation types and brought together.

10. A formulation according to Claim 9, characterized in that either one of oxadiazon and clomazone is in form of emulsifiable concentrate (EC) oil-in-water or water-in-oil emulsion (EW), suspension concentrate (SC), micro-emulsion concentrate (ME), capsule suspension or microencapsulation (CS), oil-based concentrate (OD, ODC), solutions (SL) and all of the other conventional liquid formulations, water dispersible granule (WDG, WG), soluble granule (SG), wettable powder (WP), dust (D), granule (G), effervescent granule (E. Gr), tablet (Tb), water soluble package (WSP) and all of the other conventional solid formulations, wherein oxadiazon and clomazone are in the same form.

11. A formulation according to Claim 1 , characterized in that the said oxadiazon and clomazone molecules are prepared together in the same dosage form.

12. A formulation according to Claim 11, oxadiazon and clomazone are formulated in a form selected from emulsifiable concentrate (EC) oil-in-water or water-in-oil emulsion (EW), suspension concentrate (SC), micro-emulsion concentrate (ME), capsule suspension or microencapsulation (CS), oil-based concentrate (OD, ODC), solutions (SL) and all of the other conventional liquid formulations, water dispersible granule (WDG, WG), soluble granule (SG), wettable powder (WP), dust (D), granule (G), effervescent granule (E. Gr), tablet (Tb), water soluble package (WSP) and all of the other conventional solid formulations.

13. A formulation according to any one of the preceding Claims 1-12, characterized in that the amount of the said oxadiazon used is 0.001-60%, preferably 5-50% and most preferably 10-45% by weight.

14. A formulation according to any one of the preceding Claims 1-13, characterized in that the amount of the said clomazone used is 0.0024-96%, preferably 0.5-70% and most preferably 1- 60% by weight.

15. A formulation according to any one of the preceding Claims 1-14, characterized in that other chlorophyll inhibitor or photosynthesis inhibitor herbicides and also HRAC (Herbicide Resistance Action Committee) WSSA (weed Science Society of America) Group: 5, 6, 7, 9, 10, 1 1, 12, 13, 14, 15 and also one or more molecules selected from the group of benzobicyclon, butachlor, oxadiargyl, pretilachlor, thiobencarb, pentrazamide, quinclorac, paraquat, diquat, quinmerac, Oxyflourfen, amitrole, aclonifen, acifluorfen-Na, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, azafenidin, carfentrazone-ethyl, sulfentrazone, pyraclonil, profluazol, flufenpyr-ethyl, benzfendizone, butafenacil, pentoxazone, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, beflubutamid, fluridone, flurochloridone, flurtamone, benzofenap, pyrazolynate, pyrazoxyfen, isoxachlortole, isoxaflutole, fluthiacet-methyl, thidiazimin, norflurazon, glufosinat, fenklorin, pendimetalin, fenoksaprop, mesotrione, tembotrione, topramezone, isoxaflutole, ethoxysulfuron, metsulfuron, klorimuron, safener, azimsulfuron, metsulfuron methyl, chlorimuron ethyl, oxaziclomefone molecules are used as an alternative to either one of the said oxadiazon or clomazone.

16. A formulation according to Claim 15, characterized in that the amount of alternative molecules used is 0.001-60% by weight and 0.0024-96% by weight when they are used as an alternative to oxadiazon and clomazone, respectively.

17. A formulation according to any one of the preceding Claims 1-14, characterized in that other chlorophyll inhibitor or photosynthesis inhibitor herbicides and also HRAC (Herbicide Resistance

Action Committee) WSSA (weed science society of America) Group: 5, 6, 7, 9, 10, 1 1, 12, 13, 14, 15 and also one or more molecules selected from the group of benzobicyclon, butachlor, oxadiargyl, pretilachlor, thiobencarb, pentrazamide, quinclorac, paraquat, diquat, quinmerac, Oxyflourfen, amitrole, aclonifen, acifluorfen-Na, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, azafenidin, carfentrazone-ethyl, sulfentrazone, pyraclonil, profluazol, flufenpyr-ethy, benzfendizone, butafenacil, pentoxazone, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, beflubutamid, fluridone, flurochloridone, flurtamone, benzofenap, pyrazolynate, pyrazoxyfen, isoxachlortole, isoxaflutole, fluthiacet-methyl, thidiazimin, norflurazon, glufosinat, fenklorin, pendimetalin, fenoksaprop, mesotrione, tembotrione, topramezone, isoxaflutole, ethoxysulfuron, metsulfuron, chlorimuron, safener, azimsulfuron, metsulfuron methyl, chlorimuron ethyl, oxaziclomefone molecules are used as in addition to the said oxadiazon and clomazone.

18. A formulation according to Claim 17, characterized in that the amount of molecule or molecules used in addition to the said oxadiazon and clomazone is 0.001-72% by weight.

19. A formulation according to any one of the preceding Claims 1-18, characterized in that the said formulation comprises at least one inactive agent selected from the group of emulsifier mix, solvent, antimicrobial preservative, antifoam, antifreeze, reactant 1 , reactant 2, reactant 3, stabilizer and carrier in addition to the said oxadiazon and clomazone.

20. A formulation according to Claim 19, characterized in that the amount of the said emulsifier mix used is 0.001-35%, preferably 0.01-30% and most preferably 0.1-26% by weight.

21. A formulation according to Claim 20, characterized in that the said formulation comprises one or more emulsifiers selected from the group of amine ethoxylates, EO/PO block polymers, ether sulfates, saturated alcohol alkoxylates, saturated alcohol ethoxylates, sorbitan ester ethoxylates, tributylphenol ethoxylates, phosphate esters, tristyrylphenol ethoxylates, sulfonation products, polycondensation products, nonylphenol ethoxylates, alkyl benzene sulfonates, castor oil ethoxylates, EO/PO alkoxylation products, saturated alcohol ethoxylates, olein sulfonates and sulfosuccinate.

22. A formulation according to Claim 21, characterized in that the said emulsifier used is tristyrylphenol ethoxylate and nonylphenol ethoxylate.

23. A formulation according to Claim 22, characterized in that the ratio of tristyrylphenol ethoxylate to nonylphenol ethoxylate is 1:1.

24. A formulation according to Claim 19, characterized in that the said formulation comprises one or more solvents selected from the group of hydrocarbons such as xylene, benzene, toluene, cyclohexane, solvesso 100, solvesso 150, solvesso 200 and exxsol series in addition to herbal oils derived from oily seeds and ethyl and methyl esters thereof and herbal terpenes.

25. A formulation according to Claim 24, characterized in that the amount of said solvent used is 1- 60%, preferably 3-50% and most preferably 5-34% by weight.

26. A formulation according to Claim 19, characterized in that the amount of said antimicrobial preservative used is 0.0001-59%, preferably 0.005-50% and most preferably 0.1-27% by weight.

27. A formulation according to Claim 19, characterized in that the amount of said antifoam used is 0.001-60%, preferably 0.05-50% and most preferably 0.1-32% by weight.

28. A formulation according to Claim 19, characterized in that the amount of the said reactant 1 used is 0.001-70%, preferably 0.05-50% and most preferably 0.02-25% by weight.

29. A formulation according to Claim 19 or Claim 28, characterized in that the said formulation comprises the Reactant 1 selected from a group consisting of compounds that contain isocyanate functional group such as methyl isocyanate, methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexyl isocyanate (HMDI) or isoprene diisocyanate (IPDI).

30. A formulation according to Claim 19, characterized in that the amount of the said reactant 2 used is 0.001-60%, preferably 0.05-50% and most preferably 0.21-28% by weight.

31. A formulation according to Claim 19, characterized in that the amount of the said reactant 3 used is 0.001-70%, preferably 0.05-50% and most preferably 0.15-19% by weight.

32. A formulation according to Claim 19 or Claim 30 or Claim 31 , characterized in that the said reactant 2 and reactant 3 are selected from among the substances that contain one of the primary, secondary or tertiary amine groups.

33. A formulation according to Claim 19, characterized in that the amount of the said stabilizer used is 0.0001-30%, preferably 0.05-20% and most preferably 0.02-12% by weight.

34. A formulation according to Claim 33, characterized in that the said stabilizer is selected from a group of xanthan gum, guar gum, gum Arabic, carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose.

35. A formulation according to Claim 32, characterized in that the said reactant 2 and reactant 3 are selected from a group of ethylamine, ethylene diamine, diethylene triamine, Methylene tetramine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine.

36. A method for production of a formulation according to any one of the preceding Claims 1-35, characterized in that the said method comprises the following steps:

• Preparation of an emulsifiable Oxadiazon solution by mixing oxadiazon, solvent, antioxidant preservative and the capsule reactant 1 ,

• Preparation of the water phase of the emulsion by adding the emulsifier mix, antifreeze, antimicrobial preservative and antifoam into water,

• Addition of the reactant 2 and reactant 3 into the emulsion prepared

• Conditioning of the mixture and

• Adjusting the viscosity with the help of stabilizer.

37. A composition according to Claim 1, characterized in that the said composition is used for management of all narrow- and broad-leaved weeds such as Echinochloa crus-galli, Cyperus spp., Echinochloa oryzoides, Alisma spp., Digitaria spp., Lindernia spp., Diplachne (leptochloa) spp. Red rice, Panicum spp. Echinochloa spp.

38. A method for application of a composition according to Claim 1, characterized in that the said method comprises:

(i) Application of the oxadiazon and clomazone combination on the field to be cultivated right after harrowing the soil prior to planting rice,

(ii) Irrigation of the field to be cultivated within minimum 1 day and preferably 4 days from application of the invention,

(iii) Spreading seeds within minimum one (1) day, preferably four (4) days and most preferably six (6) days from irrigation of the cultivation field.

39. A method of application according to Claim 38, characterized in that the said oxadiazon active agent is applied at a dose between 3.5 g a.i/da and 210 g a.i/da and preferably between 17.5 g a.i/da and 70 g a.i/da on the field.

40. A method of application according to Claim 38, characterized in that the said clomazone active agent is applied at a dose between 3.5 g a.i/da and 280 g a.i/da and preferably between 15 g a.i/da and 95 g a.i/da on the field.

41. A method of application according to Claim 38, characterized in that the seeds broadcasted onto the soil in step (iii) of the said method are the seeds that are germinated by soaking in a container filled with water at least 48 hours before application.

42. A method of application according to Claim 38, characterized in that at least one other active agent is used in addition to the combination of clomazone and oxadiazon at the time of the said application.

43. A method of application according to Claim 42, characterized in that the said at least one other active agent is one or more molecules or a combination of molecules selected from the group of WSSA Group: 5, 6, 7, 9, 10, 11, 12, 13, 14, 15 or benzobicyclon, butachlor, oxadiargyl, pretilachlor, thiobencarb, pentrazamide, quinclorac, paraquat, diquat, quinmerac, Oxyflourfen, amitrole, aclonifen, acifluorfen-Na, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, azafenidin, carfentrazone-ethyl, sulfentrazone, pyraclonil, profluazol, flufenpyr-ethyl, benzfendizone, butafenacil, pentoxazone, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, beflubutamid, fluridone, flurochloridone, flurtamone, benzofenap, pyrazolynate, pyrazoxyfen, isoxachlortole, isoxaflutole, fluthiacet-methyl, thidiazimin, norflurazon, glufosinat, mesotrione, tembotrione, topramezone, isoxaflutole, fenklorin, pendimetalin, fenoksaprop, ethoxysulfuron, metsulfuron, klorimuron, safener, azimsulfuron, metsulfuron methyl, chlorimuron ethyl, oxaziclomefone, norflurazon, clomazone and isoxaflutole.

44. An herbicide composition for weed management, characterized in that 4.8 units of clomazone is used for 0.12 to 6.0 units of oxadiazon.