(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2017/026957 Al 16 February 2017 (16.02.2017) P O P C T

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every A01N 43/82 (2006.01) A01P 13/02 (2006.01) kind of national protection available): AE, AG, AL, AM, A01N 25/28 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, (21) International Application Number: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, PCT/TR201 6/0001 17 HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, (22) International Filing Date: KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, 15 August 2016 (15.08.2016) MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (25) Filing Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, (26) Publication Language: English TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: (84) Designated States (unless otherwise indicated, for every 2015/10063 13 August 2015 (13.08.2015) TR kind of regional protection available): ARIPO (BW, GH, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, (71) Applicant: ENTOVEST ILAC KlMYA VE TEKNO- TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, LOJi ARASTIRMA MERKEZI SANAYI TICARET TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, LiMITED SIRKETi [TR/TR]; Tuzla Kimya Sanayiciler DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, Organize Sanayi Bolgesi, Melek Aras Bulvan No:33, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, Tuzla/Istanbul (TR). SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). (72) Inventor: TUNCAY, Yildiztekin; Tuzla Kimya Sanayi ciler Organize Sanayi Bolgesi, Melek Aras Bulvan No:33, Published: Tuzla/Istanbul (TR). — with international search report (Art. 21(3)) (74) Agent: MENDES, Pinar; info Patent Marka Ve Fikri — before the expiration of the time limit for amending the Haklari Dan. Ltd. Sti, Barbaras Mah. Deluxia Suits No: 3 claims and to be republished in the event of receipt of D :163, Atasehir/Istanbul (TR). amendments (Rule 48.2(h))

© o- (54) Title: FORMULATION OF OXADIAZON WITH NO PHYTOTOXICITY IN RICE (57) Abstract: The present invention is intended to eliminate the problems experienced in the prior art of oxadiazon, which is a chemical known for weed management in paddy fields in the agriculture industry but not used due to phytotoxicity in paddy fields and accumulation in soil, through capsule suspension formulation of this molecule and to use this formulation in the relevant in - dustry. FORMULATION OF OXADIAZON WITH NO PHOTOTOXICITY IN RICE

TECHNICAL 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 with five different cultivation systems in the world depending on the water regimen. Different types of rice cultivated using 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 there 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).

Rice is generally grown in water-fed parcels (beds). Rice planting is performed by planting the seeds into dryland or wetland. Difference in such planting method results from several factors such as regional practices, climatologic conditions, availability or unavailability of adequate water and geographical conditions.

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 it requires 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 long-term working in such fields 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 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 a new formulation and a new method developed with oxadiazon, a different herbicide molecule, to eliminate such treat.

The present invention is intended to eliminate the problems experienced in the prior art of oxadiazon, which is a chemical known for weed management in paddy fields in the agriculture industry but not used due to phytotoxicity in paddy fields and accumulation in soil, through capsule suspension formulation of this molecule and to use this formulation in the relevant industry.

With the present invention, a capsule suspension formulation was developed from oxadiazon molecule, the new form of oxadiazon herbicide was tried in weed management in rice cultivation fields, it was observed that the high rice phytotoxicity observed in the formulations of the prior art of the subject molecule was not present in the formulation subject to the invention and surprisingly high level of action was obtained in weed management by using lower doses. BACKGROUND OF THE INVENTION

Oxadiazon is an herbicide that is a chlorophyll inhibitor and it chemical name is 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl)-l,3,4-oxadiazol-2(3H)-one.

Oxadiazon is a highly persistent herbicide with a half life of 3-6 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 (emulsion concentrate (EC), Water-soluble Powder (WP), Granule (G) and other solid or liquid formulations "other than the capsule formulation") have been used in management of many weed types in cultivation of various crops aside from rice.

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 the seed. Recently, solid or liquid formulations other than the oxadiazon capsule formulation subject to the invention have been used in rice cultivation, even if not commonly used. In the state of the art, particularly in EC formulations of oxadiazon, the active agent is completely free at the time it reaches the area of application. Considering the free state of this molecule along with its persistence in soil, it is obvious that the product is not suitable for weed management in rice cultivation. In other words, the effect of the free molecule that lasts for months means an attack dose that lasts for months; and such attack dose is harmful to the rice as much as the weed. Therefore, conventional formulation types of such products are not used unless rice farmers are completely out of solutions.

One of the prior arts is use of EC formulation type of oxadiazon in weed management in rice cultivation. In practices involving this formulation type, severe and intolerable phytotoxicity were observed in rice. Many researches were conducted by the inventors regarding new formulation techniques for the active agent oxadiazon herbicide and different application methods in order to eliminate the severe phytotoxicity and seed loss resulting from the application of the prior art. As a result of such researches, it was discovered that capsule suspension of the herbicide can be used in weed management in rice cultivation industry. In the prior art, formulations other than the capsule suspension were tried and problems were experienced in the germination of the rice. In the prior art, the field where the rice will be planted is leached at least twice after application of oxadiazon in order to eliminate such problem. Such process not only increases the cost but also decreases the level of success of weed management. The reason is that the leaching process triggers growth of weeds while decreasing the effective dose on the weed since oxadiazon is leached away. Furthermore, the period between soil preparation and planting cannot be kept long due to several reasons. Such period varies between 1 and 3 days. It is because the meteorological conditions do not allow the rice farmer ample time during such busy period of the farmer. Therefore, it is not possible to use in the industry the conventional formulae of Oxadiazon other than the CS formulations except for unavoidable circumstances.

In the prior art, the oxadiazon that is found in a free state after Oxadiazon EC is applied is adsorbed on the upper colloids. Oxadiazon found in the upper layers of soil contacts the rice seeds during planting the rice. Oxadiazon that is strongly adsorbed on the upper layers of the soil is completely in a free state. It is in direct contact with rice seeds upon planting and such contact has an attack dose effect, which results in loss of germination strength of the rice and its inability to germinate.

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 35-45% 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.

During that period, the rice is submerged, and the application is very difficult and expensive. Since aerial applications are forbidden due to environmental awareness, the problem becomes bigger. 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.

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 to weed has become a major problem in weed management in rice cultivation almost all around the world. Resistance of weeds cannot be prevented despite application of such herbicides in doses increased by 4-5 times.

In the prior art, molecules having a new action mechanism other than the action mechanism mentioned above were researched; as a result, oxadiazon was used with a different action mechanism. The results from the experiments conducted were recorded at every location. All results were parallel to each other; and better results were obtained in weed management by using oxadiazon when compared to using FOB, ALS, auxin hormones and herbicides acting in contact. In such experiments, the effect on rice germination was also assessed in addition to the weed management.

In the prior art, as a result of the applications performed, Oxadiazon Emulsion Concentrate (EC) formulation severely damaged the rice and intolerable levels of phytotoxicity were observed in the cultivation fields where oxadiazon was used.

In the prior art, the soil was leached for at least 2 times after application in order to prevent the phytotoxicity in rice; however, the observed levels of mortality of rice seeds were intolerable despite the leaching process.

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 the EC form of oxadiazon was applied; however, this could not also prevent growth of weeds. As the results of the experiments indicate, climatic conditions were not always favorable for postponing the planting and the effective dose was lost since oxadiazon was exposed to direct sunlight in the soil. Effective dose 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. When the starting dose is increased, this may prevent germination of the rice seeds. 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 the prior art, high starting doses resulted in chemical pollution of non-target areas when the doses were leached. In particular, release of petroleum-derivative solvents and emulsifiers found in the EC formulation (emulsion concentrate) to the nature resulted in ecologic pollution. Such chemical pollution was eliminated thanks to the present invention. It is because the capsule formulation subject to the invention is water-based and safer for the environment compared to the previous formulations.

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 EC). 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 case of using Oxadiazon EC, which is 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 EC 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 conventional application technique of Oxadiazon EC, apart from the reasons mentioned above (leaching, conditioning) the performance of the formulation is also insufficient. The comparative trial performed using Oxadiazon EC formulation and the formulation of the present invention and the results of the trial are given below in the section where the invention is proved in detail. According to the results obtained, the invention shows greater performance at lower doses- at least 20% less.

OBJECTS OF THE INVENTION

In consideration of the prior art described above, it is seen that new formulations of the oxadiazon molecule is needed for use in weed management in cultivation of rice. Accordingly, the inventors aim to develop an oxadiazon formulation for management of the weeds that grow in paddy fields.

In a sense, the inventors aim at developing a method that will allow application of the capsule suspension (CS) formulations containing oxadiazon active agent without causing phytotoxicity and damage to different species of plants by drifting in the soil.

The inventors also aim to develop a formula that will eliminate the disadvantages of the herbicides used in weed management in rice cultivation. In this context, the inventors aim at developing a product that will manage the weeds and will be economical in terms of the environment, efficiency, cost and labor by means of developing a formula to manage the weeds at germination stage by using the oxadiazon active agent, to which the weeds have no resistance, prior to transplanting. The formulations according to the present invention prevent use of generally petroleum-based solvents and emulsifiers that are released from rice parcels into underground and surface waters.

The inventors have discovered that the weed problem in rice cultivation is managed, the rice seeds are not damaged and the yield of the cultivated field is increased by using the capsule suspension form of Oxadiazon, the details of which are described below.

SUMMARY OF THE INVENTION

The problem that the invention aims to solve is the inability to use oxadiazon due to phytotoxicity.

This problem has been solved by using the oxadiazon active agent in CS formulation for weed management in rice cultivation. By using oxadiazon CS formulation, a higher effect was obtained at a lower dose when compared to the conventional formulations in weed management, and the phytotoxicity problem in rice caused by the conventional formulations was eliminated. The invention relates to the development of oxadiazon capsule formulation and the method of application of the technology developed in weed management in rice cultivation.

The problem was solved with the safe formulation types of oxadiazon and their use.

Oxadiazon CS formulation is used in management of weeds indicated in this specification, for example Echinochloa spp. and particularly Echinochloa crus-galli (L Beauv.), Cyperus spp. and particularly Cyperus difformis L., Alisma spp. and particularly Alisma plantago-aquatica L., Echinochloa spp. and particularly Echinochloa oryzoides (Ard.) F. and other narrow and large leaved weeds.

Aside from the Oxadiazon CS formulation, CS, ZW, ZE, ZC, EW,MC, ES, SE, ME, SC, CF, etc. formulations have the same effect.

DETAILED DESCRIPTION OF THE INVENTION

Other formulation types of oxadiazon (emulsion concentrate (EC), Water-soluble Powder (WP), Granule (G) and other conventional formulations) have been used in management of many weed types in cultivation of various crops aside from rice. Recently, solid or liquid formulations other than the capsule formulation of oxadiazon have been tried in rice cultivation, even if not commonly used. However, considering the free state of the active agent of such formulations along with its persistence in soil up to 3-6 months, major phytotoxicity takes place in rice during applications both before and after planting and the development of rice stops for almost one month. Therefore, rice farmers do not use the conventional formulation types of this molecule unless they are completely out of solutions.

The present invention has both eliminated the phytotoxicity problem and made it possible to obtain greater yields at lower doses. Such advantages have been obtained by using the capsulation formulation of the Oxadiazon molecule subject to the present invention. The invention relates to the problem-free use of oxadiazon and was discovered by using the CS formulation type of Oxadiazon in weed management having integrated the formulation with a new method of application.

The present invention relates to the capsule suspension form of the oxadiazon molecule suitable for use in rice cultivation fields.

From another angle, the present invention relates to the capsule suspension formulations that contain at least one inactive agent in addition to the oxadiazon.

The present invention comprises the encapsulation of the active agent oxadiazon with all of the conventional methods to obtain the capsule suspension formulation. The table below describes the preferred percentage and contents and interfacial polymerization as the preferred technique without limiting the scope of the invention.

The table below shows the general and preferred percentages of the components that constitute the present invention by weight.

Table . General and preferred percentages of the components that constitute the invention

The term "emulsifier mix" used within the scope of the present invention comprises both the mix that is composed of the combination of more than one emulsifier and the emulsifier composed of a single emulsifier. Such emulsifier or emulsifiers may be from ionic, anionic and nonionic groups or a combination of such groups. Emulsifier used in the method of the present invention may be one or more selected from the group of amine ethoxylates, ethylene oxide (EO) / propylene oxide (PO) block polymers, ether sulfates, saturated alcohol alkoxylates, 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. In case of using more than one emulsifier, such emulsifiers may be used in the same or different amount. 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.

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. Solvents, which are not soluble in water, are used within the scope of the invention. The solvents that may be used in the formulation subject to the invention may be selected from the group of xylene, benzene, toluene, cyclohexane, solvesso 100, solvesso 150, solvesso 200 and exxsol series hydrocarbons in addition to herbal oils derived from oily seeds and ethyl and methyl esters thereof and herbal terpenes. The solvent used in the method of the present invention may be one selected from the group mentioned above or a combination of at least two or more solvents selected from the same group. In case of using two different solvents, such solvents may be used in same or different amounts. The preferred solvent used in the formulation is xylene.

The antioxidant preservative indicated in the Table is butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA).

The antifreeze indicated in the Table is the glycol derivative additives that prevent freezing at low temperatures, which is an application known in water-based pesticide formulations. The antifreeze used in the formulations according to the present invention may be selected from the group of ethylene glycol, monopropylene glycol, dipropylen glycol, diethylene glycol and glycerin. The preferred antifreeze used in the formulation is monopropylene glycol.

The reactant 1 indicated in the Table is the 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. In this context, the reactant 1 may be selected from the group of methyl isocyanate, methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexyl isocyanate (HMDI) or isoprene diisocyanate (IPDI).

The reactant 1 and reactant 2 indicated in the Table are the amines that create a polyurea 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 reactant 2 and reactant 3 that may be used within the scope of the present invention are selected from the group of ethylamine, ethylene diamine, diethylene triamine, triethylene tetramine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine. Reactant 2 and reactant 3 may be the same or two different molecules selected from the abovementioned group.

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. The stabilizer used in the formulation of the present invention may be selected from the group of xanthan gum, guar gum, gum Arabic, carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose. The preferred stabilizer used in the formulation is xanthan gum.

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.

In the formulations according to the present invention, the amount of oxadiazon used is 0.001 - 85% by weight, preferably 0.1 - 70% by weight, most preferably 1 - 60% by weight and for example 20% by weight.

In the formulations according to the present invention, the amount of emulsifier mix used is 0.01 - 35% by weight, preferably 0.1 - 30% by weight, most preferably 3 - 15% by weight and for example 6% by weight. In the formulations according to the present invention, the amount of solvent used is 1 - 60% by weight, preferably 5 - 40% by weight, most preferably 10 - 35% by weight and for example 22% by weight.

In the formulations according to the present invention, the amount of antimicrobial preservative used is 0.0001 - 59% by weight, preferably 0.001 - 40% by weight, most preferably 0.1 - 30% by weight and for example 0.3% by weight.

In the formulations according to the present invention, the amount of antifoam used is 0.001 - 60% by weight, preferably 0.1 - 40% by weight, most preferably 0.1 - 30% by weight and for example 1% by weight.

In the formulations according to the present invention, the amount of antifreeze used is 0.01 - 60% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 4% by weight.

In the formulations according to the present invention, the amount of reactant 1 used is 0.001 - 70% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 5% by weight.

In the formulations according to the present invention, the amount of reactant 2 used is 0.001 - 60% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 2% by weight.

In the formulations according to the present invention, the amount of reactant 3 used is 0.001 - 70% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 1% by weight.

In the formulations according to the present invention, the amount of stabilizer used is 0.0001 - 30% by weight, preferably 0.0005 - 25% by weight, most preferably 0.001 - 20% by weight and for example 0.08% by weight.

In addition to the abovementioned inactive agents found in the Oxadiazon CS formulation to be used in the method of the present invention, different inactive agents may also be used. Such additional inactive agents may be selected from the group of viscosity modifier, density modifier, distributor, suspending agent, solvent, etc.

The viscosity modifier may be selected from a group including but not limited to guar gum, xanthan gum, carrageenan, alginate, hydroxypropyl methylcellulose, etc.

The density modifier may be selected from a group including but not limited to carrageenan, pectin, gelatin, polyethylene glycol, polyvinyl alcohol, hydroxypropyl methylcellulose, carboxymethyl cellulose, etc.

The distributor may be selected from a group including but not limited to ammonium lauryl sulfate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium stearate, polyethylene glycol, etc.

The solvent may be selected from a group including but not limited to water or organic solvents, for example ethanol, methanol, isopropyl, propanol, butylene, hexane, heptane, benzene, toluene, xylene, Solvesso, triethylamine, dimethylsulfoxide, dimethylformamide or a combination thereof.

On the other hand, the present invention relates to a production method to be used to prepare the capsule suspension formulation of oxadiazon. The subject production 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,

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

• Slow addition of the other reactants, which are reactant 2 and reactant 3, into the emulsion prepared,

• Conditioning of the mixture to finalize the polymerization reaction initiated and then adjusting the viscosity with the help of stabilizer.

On the other hand, the present invention relates to a method to be employed during application of the formulations of oxadiazon capsule suspension to paddy fields. The inventors have aimed to develop a method of application that allows use of oxadiazon molecule by means of encapsulation without damaging the rice in paddy fields.

The method according to the present invention comprises the following steps:

- Rice seeds inside sacks or similar materials are soaked in water to break the seed coats and render them ready for germination. This step may be skipped, if preferred, and rice seeds may be planted without breaking their coats in this sense, the method that does not involve breaking the seed coats is also included in this patent application.

- The soil where the seeds will be planted is harrowed.

- Oxadiazon capsule suspension (CS) formulation is applied to the soil prepared.

- The soil is watered and the seeds are transplanted minimum 24 hours, preferably minimum 72- 168 hours after applying the formulation.

This way, the inventors have observed that the rice seeds are not in direct contact with the encapsulated oxadiazon in high doses, and thus, germination and growth problems of the rice resulting from high doses of active agent are eliminated. By means of slow release, the oxadiazon capsules contacting the weed seeds in the soil will manage the weed seeds that will emerge gradually.

Detailed description of the application method of the invention

The present invention is also a method regarding application of the capsule suspension formulation of oxadiazon molecule in order to dispose of weeds in paddy fields comprising (i) application of capsule suspension (CS) formulation of oxadiazon to the area to be cultivated right after harrowing the soil before transplanting the rice, (ii) irrigation of the area to be cultivated at least 24 hours after applying the capsule suspension formulation of oxadiazon and (iii) transplanting the seeds minimum one (1) day, preferably four (4) days, most preferably six (6) days after irrigating the area to be cultivated.

Below given are certain essentials regarding the application of the method subject to the invention:

1) The soil is harrowed; the success of oxadiazon CS is extraordinarily high if the area to be cultivated is harrowed.

2) The oxadiazon CS should be applied right after harrowing without waiting.

3) Recommended dose of oxadiazon CS is pulverized on the surface of the soil using t-jet nozzles. 4) Oxadiazon CS is added in 20-40 liters of water per decare. The device should be calibrated for dose adjustment.

5) The soil should never be harrowed after oxadiazon CS is applied.

6) The soil should be irrigated minimum one (1) day, preferably four (4) days after applying the Oxadiazon CS; and the seeds should be transplanted minimum one (1) day and most preferably 6 days after the water is released.

7) Drying durations should not be kept long so that oxadiazon CS can show full performance.

8) Extreme drying should be avoided not allowing the surface of the soil to crack.

In the subject method, rice seeds put in a container are soaked in water to break the coats of the seeds. The said container may be a sack, wooden container, plastic container, etc. Breaking of the coats is not necessarily performed.

In the method described above, the dose of the active agent oxadiazon (for CS formulation) to be applied to the area to be cultivated may be between 5 g a.i/da and 300 g a.i/da, preferably 25 g a.i/da and 100 g a.i/da, and most preferably 30 g ai/da and 85 g a.i/da.

Optionally, the soil may be harrowed before applying the Oxadiazon CS formulation.

The Oxadiazon active agent to be used within the scope of the present invention, which is in the form of emulsion concentrate (EC), may also be in the form of encapsulated suspension (MC / ES / CS). The Oxadiazon active agent to be used within the scope of the present invention, which is in the form of microcapsule suspension (CS) that provides controlled release, may also be in the form of other formulation types that provide controlled release being microcapsule suspension for seed treatment (CF), microcapsule concentrate (MC), microcapsule + oil-in-water emulsion (ZW) mixture, microcapsule + suspension concentrate mixture (ZC) or microcapsule + suspension concentrate + oil-in-water emulsion mixture (ZE). The dosage and form of the active agent, which is not limited to those mentioned herein, may be in other solid or liquid formulations.

The present invention, comprising the capsule suspension formulation of Oxadiazon, also comprises other water-based mono and multi formulations.

The present invention may be used in other agricultural or non-agricultural areas where phytotoxicity or effectiveness problems are experienced in use of oxadiazon molecule. The invention also comprises the application in weed management for different agricultural produces and on non-agricultural areas such as lawns.

Since the present invention manages weeds, in particular Cyperus spp. and certain Echinochloa species by >90%, the yield obtained from the areas where the invention is applied is greater than that of other areas.

The inventors have observed as a result of their studies that the method subject to the invention have unexpectedly increased the effectiveness of the use of oxadiazon in the form of capsule suspension, and thus, a new method has been developed along with a new, cost-efficient, effective and easy-to-apply formulation in weed management in paddy fields. Therefore, the present invention relates to a method intended for the application of capsule suspension formulation of oxadiazon for application of Oxadiazon molecule in paddy fields, comprising:

1. Application of CS formulation of oxadiazon to the area to be cultivated before 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.

During the researches conducted, the inventors at first observed that weed seeds lost their germination strength by >90% upon application of Oxadiazon CS formulation in the area of cultivation prepared and a surprisingly high effectiveness was obtained in weed management. Such effectiveness was obtained at a lower dose, at least 20% less than the dose of the emulsion concentrate formulation of oxadiazon. In the applications performed, the paddy field was irrigated at least 24 hours and preferably 96 hours after application of Oxadiazon CS; and the rice seeds ready to germinate were broadcasted onto the surface of the water preferably 114 hours after such process. Thus, the rice seeds, which were half-germinated in sacks, were not affected by Oxadiazon CS (However, when the same procedure was performed using oxadiazon EC (emulsion concentrate) formulation, it was observed that the rice seeds lost their germination strength). Furthermore, Oxadiazon CS molecules, which were adsorbed on soil colloids, showed 72-day long effect against new weeds to emerge through slow and time-dependent release. Therefore, this method, which is very safe for rice, provides high effectiveness in weed management.

The abbreviations ZW, ZE, ZC, EW, MC, ES, SE, ME, CF and SC used within the scope of the present invention stand for the types of different pesticide formulations commonly known in the state of the art.

The abbreviation EW used within the scope of the present invention stands for the formulation of oil-in-water emulsion.

The abbreviation ES used within the scope of the present invention stands for the formulation of emulsion for seed treatment.

The abbreviation SE used within the scope of the present invention stands for the formulation of suspo-emulsion.

The abbreviation ME used within the scope of the present invention stands for the formulation of micro-emulsion.

The abbreviation MC used within the scope of the present invention stands for the formulation of micro-emulsion.

The abbreviation CF used within the scope of the present invention stands for the formulation of capsule suspension for seed treatment.

The abbreviation SC used within the scope of the present invention stands for the formulation of suspension concentrate (fluid concentrate).

The abbreviation CS used within the scope of the present invention stands for the formulation of capsule suspension.

The abbreviation ZC used within the scope of the present invention stands for the formulation composed of a mixture of CS and SC formulations.

The abbreviation ZE used within the scope of the present invention stands for the formulation composed of a mixture of CS and SE formulations.

The abbreviation ZW used within the scope of the present invention stands for the formulation composed of a mixture of CS and EW formulations.

In the method to be applied within the scope of the present invention, at least one different active agent can also be used in addition to the oxadiazon active agent. Such other active agent can be used in combination with oxadiazon at the same time or at another stage of the production. Such second active agent may be one or a combination selected from the group of glyphosate, paraquat, glufosinate, butachlor, pretilachlor, fenclonine, clomazone, pendimethalin, oxadiargyl, bispyribac sodium, fenoxaprop, ethoxysulfuron, metsulfuron, chlorimuron, safener, azimsulfuron, phenoxylane.

The formulation according to the invention may be used in management of weeds that cause great loss in yield, including but not limited to Echinochloa crus-galli (L Beauv.) and Echinochloa spp., Cyperus difformis L. and Cyperus spp., Alisma plantago-aquatica L. and Alisma spp., and Echinochloa oryzoides (Ard.) F. The application of the invention also comprises other narrow and large leaved weeds.

The inventors have conducted various trials using the method described in detail above. In one of the studies performed, 20% capsule suspension form of Oxadiazon active agent subject to the invention was used at doses 75 ml/da, 100 ml/da, 150 ml/da and 300 ml/da. Weed management was >90% at doses 100 and 150 ml/da.

The inventors have conducted experiments in order to prove that the formulation according to the present invention has properties that are superior to the formulations in the state of the art. Below given are the formulations of the present invention and the prior art and the joint results of the experiments conducted with the application methods. Such experiments were:

1. Conducted by Prof. Dr. Husrev MENNAN and his team from Ondokuzmayis University, Plant Protection Department during May-September 2014 in Osmancik-Crum-Turkey and Ipsala-Edirne-Turkey.

2. Conducted by Specialist Agronomist Mesut Atalay, Deniz Serdar Ozcelik and Volkan Ozturk during May-September 2013-2015 in Bafra Samsun-Turkey, Boyabat-Sinop- Turkey, Bandirma Balikesir- Turkey, Cavuskoy, Biga Balikesir- Turkey and Uzunkopru-Edirne Turkey.

3. The results in the Table are given by arithmetic averages wherein the result of each experiment does not deviate more than 5% from others.

4.

1

The invention was considered successful for passing the limit value of 90% at 30 g a.i/da dose. No measures such as leaching were taken after application. No negative results were obtained in germination compared to the control groups.

Furthermore, it is seen that, starting from the dose of 20 g a.i/da, the oxadiazon formulation subject to the invention gives better results than the formulation of the prior art known for at least one type of weed.

2

A mild phytotoxicity was observed at the selectivity dose of the invention for phytotoxicity and rice germination, and such phytotoxicity ended within 7 days. At the end of day 30, no difference was observed between the paddy field on which the herbicide was not applied and the paddy field on which the selectivity dose of the invention was applied. Leaching was not performed after application of the selectivity dose.

3

The effectiveness of the oxadiazon EC herbicide of the prior art did not go above the limit value of 90% for any type of weed when applied at the effective dose of the invention, which is 30 g a.i/da. The soil was leached once (1) after application. Furthermore, oxadiazon EC at dose 30 g ai /da showed a higher rice phytotoxicity than the selectivity dose of the invention (60 g a.i/da). During the harvest, the lengths of the control group and the rice in the area where the herbicide of the prior art (oxadiazon EC 30 g ai/da) was applied showed a difference. Since the dose applied was not the effective dose, it was not evaluated whether the application caused loss in yield.

4

The oxadiazon EC herbicide of the prior art was successful in managing certain weeds at the dose of 37.5 g a.i/da. The soil was leached twice (2) after the application. The rice showed growth deficiency of 15 days, and the yield loss during the harvest was 13%.

5

The dose 60 g a.i/da, which is the selectivity dose for the invention, was also considered as the selectivity dose for the oxadiazon EC of the prior art; the rice did not emerge despite the leaching operation performed twice (2) after the application. Since rice will not emerge in case of any possible application of high doses by the farmer, it was concluded that application of oxadiazon EC would not be suitable for weed management in rice cultivation.

It was observed that germination stopped after day 30 in a field where the formulation according to the prior art was applied at the dose effective on weeds (37,5 g a.i/da).

Embodiment of the formulation according to the invention: Tristyrylphenol ethoxylate: nonylphenol ethoxylate (1:1) 6

Xylene 22

Butylated hydroxytoluene and butylated hydroxyanisole 0.3

Antifoam 1

Monopropylene glycol 4

Methyl isocyanate 5

Trimethylamine 2

Dimethylaminopropylamine 1

Stabilizer 0,08

Water Takes up to 100%

• An emulsifiable oxadiazon solution is prepared by mixing the Oxadiazon with xylene, butylated hydroxytoluene and butylated hydroxyanisole and Methyl isocyanate, • Tristyrylphenol ethoxylate: nonylphenol ethoxylate (1:1), monopropylene glycol, butylated hydroxytoluene and butylated hydroxyanisole and antifoam are added in water to prepare the water phase of the emulsion. The oxadiazon solution prepared is emulsified in water phase with the help of a high-speed mixer. • Other reactants, namely Trimethylamine and Dimethylaminopropylamine, are slowly added into the emulsion prepared. · The mixture is left to rest to finalize polymerization initiated, and then the viscosity is adjusted with the help of stabilizer.

The scope of the invention cannot be limited to the embodiments given above, which are only intended to describe the invention. A formulation suitable for use to eliminate the weeds in rice cultivation fields, wherein said formulation: - contains oxadiazon as the active agent and - is in the form of capsule suspension. The formulation of Claim 1 wherein said formulation may be in the form of other formulation types such as ZW, ZE, ZC, EW, C, ES, SE, ME, CF and SC in addition to the capsule suspension (CS) form. The formulation of Claim 1 wherein said formulation comprises at least one inactive agent in addition to oxadiazon. The formulation of Claim 3 wherein said formulation comprises at least one inactive agent selected from the group of emulsifier, solvent, antimicrobial preservative, antifoam, antifreeze, reactant 1, reactant 2, reactant 3, stabilizer and carrier. The formulation of Claim 4 wherein said emulsifier may be a single emulsifier or a combination of more than one emulsifier. The formulation of Claim 4 or 5 wherein said emulsifier may be one or 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. The formulation of Claim 6 wherein said emulsifier is the combination of tristyrylphenol ethoxylates and nonylphenol ethoxylates. The formulation of Claim 7 wherein said tristyrylphenol ethoxylates and nonylphenol ethoxylates are used as a mixture in 1:1 ratio. 9. The formulation of any one of the Claims 6-8 wherein the amount of said emulsifier mix used is 0.01 - 35% by weight, preferably 0.1 - 30% by weight, most preferably 3 - 15% by weight and for example 6% by weight. 10. The formulation of Claim 4 wherein said solvent is selected from the group of xylene, benzene, toluene, cyclohexane, solvesso 100, solvesso 150, solvesso 200 and exxsol series hydrocarbons in addition to herbal oils derived from oily seeds and ethyl and methyl esters thereof and herbal terpenes.

11. The formulation of Claim 10 wherein said solvent is xylene. 12. The formulation of Claim 10 or 11 wherein the amount of said solvent used is 1 - 60% by weight, preferably 5 - 40% by weight, most preferably 10 - 35% by weight and for example 22% by weight. 13. The formulation of Claim 4 wherein said antioxidant preservative is butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). 14. The formulation of Claim 13 wherein the amount of said antioxidant preservative used is 0.0001 - 59% by weight, preferably 0.001 - 40% by weight, most preferably 0.1 - 30% by weight and for example 0.3% by weight. 15. The formulation of Claim 4 wherein said antifreeze is selected from the group of ethylene glycol, monopropylene glycol, dipropylen glycol, diethylene glycol and glycerin.

16. The formulation of Claim 15 wherein said antifreeze is monopropylene glycol.

17. The formulation of Claim 15 or 16 wherein the amount of said antifreeze used is 0.01 - 60% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 4% by weight. 18. The formulation of Claim 4 wherein said reactant 1 is selected from the group ofmethyl isocyanate, methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexyl isocyanate (HMDI) or isoprene diisocyanate (IPDI).

19. The formulation of Claim 18 wherein the amount of said reactant 1 used is 0.001 - 70% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 5% by weight. 20. The formulation of Claim 4 wherein said reactant 2 and reactant 3 are selected from the group of ethylamine, ethylene diamine, diethylene triamine, triethylene tetramine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine. 21. The formulation of Claim 20 wherein said reactant 2 and reactant 3 may be the same or two different molecules. 22. The formulation of Claim 20 or 2 1 wherein the amount of said reactant 2 used is 0.001 - 60% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 2% by weight. 23. The formulation of any one of the Claims 20-22 wherein the amount of said reactant 3 used is 0.001 - 70% by weight, preferably 0.05 - 30% by weight, most preferably 0.1 - 20% by weight and for example 1% by weight. 24. The formulation of Claim 4 wherein said stabilizer is selected from the group of xanthan gum, guar gum, gum Arabic, carboxymethyl cellulose, methylcellulose, hydroxypropyl cellulose. 25. The formulation of Claim 24 wherein said stabilizer is xanthan gum. 26. The formulation of Claim 24 or 25 wherein the amount of said stabilizer used is 0.0001 - 30% by weight, preferably 0.0005 - 25% by weight, most preferably 0.001 - 20% by weight and for example 0.08% by weight. 27. The formulation of Claims 1-26 wherein said formulation further comprises at least one second active agent selected from a group of glyphosate, paraquat, glufosinate, butachlor, pretilachlor, fenclonine, clomazone, pendimethalin, oxadiargyl, bispyribac sodium, fenoxaprop, ethoxysulfuron, metsulfuron, chlorimuron, safener, azimsulfuron, phenoxylane in addition to the active agent oxadiazon. 28. A method to be used to prepare the formulation of Claims 1-27 wherein 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 - Emulsification of the oxadiazon solution in water phase with the help of high-speed mixer, - Slow addition of the other reactants, which are reactant 2 and reactant 3, into the emulsion prepared, Conditioning of the mixture to finalize the polymerization reaction initiated and then adjusting the viscosity with the help of stabilizer. 29. A method to be used for application of capsule formulation of oxadiazon in paddy fields wherein said method comprises: - Harrowing of the soil to be cultivated - Application of capsule suspension (CS) formulation of oxadiazon to the soil prepared The soil is watered and the seeds are transplanted minimum 24 hours, preferably minimum 72-168 hours after applying the formulation

30. The method of Claim 29 wherein the oxadiazon capsule suspension is applied right after harrowing without waiting. 31. The method of Claim 29 or 30 wherein oxadiazon CS is pulverized on the surface of the soil using t-jet nozzles. 32. The method of any one of the Claims 29-3 1 wherein oxadiazon capsule suspension is added in 20-40 liters of water per decare. 33. The method of any one of the Claims 29-32 wherein soil is irrigated minimum one (1) day, preferably four (4) days after applying the Oxadiazon CS and the seeds are transplanted minimum one (1) day and most preferably 6 days after the water is released. 34. The method of any one of the Claims 29-33 wherein the dose of the active agent oxadiazon to be applied to the area to be cultivated is between 5 g a.i/da and 300 g a.i/da, preferably 25 g a.i/da and 100 g a.i/da, and most preferably 30 g ai/da and 85 g a.i/da. 35. Oxadiazon formulation of any one of the Claims 1-27 wherein said oxadiazon formulation is used in management of weeds Echinochloa crus-galli (L Beauv.) and Echinochloa spp., Cyperus difformis L. and Cyperus spp., Alisma plantago-aquatica L. and Alisma spp., Echinochloa oryzoides (Ard.) F. and other narrow and large leaved weeds. INTERNATIONAL SEARCH REPORT

PCT/TR2016/000 117

I NV . A91N43/82 A0 1N25/28 AQ1 P13/G2 ADD .

A01N

EPO- I nternal , WPI Data

WO 00/60944 Al (AVENTI S CROPSCI ENCE SA 1-35 [ FR] ; I KEDA KAORU [ J P] ; SUZU KI HI SATO [ P] 19 October 2000 (2000- 10- 19 ) tabl e 2

US 2015/208653 Al ( BECH ER DAV I D Z [US] ) 1- 5 , 35 30 Jul y 2015 [ 2015 -07 -30 ) paragraph [00041 ; c l a i ms 1 45 ; ex

□

2 1 December 2016 04/01/2017

Bertrand Franck INTERNATIONAL SEARCH REPORT International application No Information on patent Tamlly members PCT/TR2016/000 117

Patent document Publication Patent family Publication cited in search report date member(s) date

WO 0060944 Al 19 - 10-2000 A R 023469 Al 04-09 2002 AT 27534 1 T 15 - 09 2004 AU 5064900 A 14- 11 2000 B R 00106 13 A 28-05 2002 CN 1365253 A 21-08 2002 CO 5231 18 1 Al 27- 12 2002 DE 60013578 Dl 14- 10 2004 EP 116892 1 Al 09 - 01 2002 ES 2228532 T3 16- 04 2005 J P 4750949 B2 17 - 08 20 11 J P 2000297002 A 24- 10 2000 J P 2002541 163 A 03 - 12 2002 PT 116892 1 E 31- 01 2005 T W 552 112 B 11-09 2003 W0 0060944 Al 19 - 10 2000

US 20 15208653 Al 30-07 -2015 AU 2015209073 Al 04-08-20 16 CA 2937505 Al 30-07 -20 15 CN 105960166 A 21-09 -20 16 EP 3107384 Al 28- 12 -20 16 US 2015208653 Al 30-07 -20 15 UY 35968 A 31-08-20 15 W0 2015 1130 15 Al 30-07 -20 15