WO 2017/061959 Al 13 April 2017 (13.04.2017) P O P C T

Home , Triisopropylamine

(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 2017/061959 Al 13 April 2017 (13.04.2017) P O P C T

(51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every A01P 7/00 (2006.01) A01N 25/28 (2006.01) kind of national protection available): AE, AG, AL, AM, A01P 7/02 (2006.01) A01N 25/04 (2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, A01P 7/04 (2006.01) A01N 43/90 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, A01P 5/00 (2006.01) A01N 53/06 (2006.01) DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, EST, IR, IS, JP, KE, KG, KN, KP, KR, (21) International Application Number: KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, PCT/TR2015/000350 MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (22) International Filing Date: PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, 2 December 2015 (02.12.2015) SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (25) Filing Language: English (84) Designated States (unless otherwise indicated, for every (26) Publication Language: English kind of regional protection available): ARIPO (BW, GH, (30) Priority Data: GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, 2014/14665 4 December 2014 (04. 12.2014) TR TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, (71) Applicant: ENTOVEST ILAC KlMYA V E TEKNO- DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LOJi ARASTIRMA MERKEZI SANAYI TICARET LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, LiMITED SlRKETi [TR/TR]; Tuzla Kimya Sanayiciler SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, Organize Sanayi Bolgesi Melek Aras Bulvari No:33, GW, KM, ML, MR, NE, SN, TD, TG). Tuzla/Istanbul (TR). Published: (72) Inventor: YILDIZTEKlN, Tuncay; Tuzla Kimya Sanayi — with international search report (Art. 21(3)) ciler Organize Sanayi Bolgesi Melek Aras Bulvari No:33, Tuzla/Istanbul (TR).

(74) Agent: UZAN, Ugur; Erk Patent Marka ve Fikri Haklar Dan. Ltd. Sti., Muminderesi Sok. Hak Apt. No:32 K:2 D:4, Sahrayicedit, Kadikoy/Istanbul (TR).

- (54) Title: A PESTICIDE COMPOSITION COMPRISING A COMBINATION OF BIFENTHRIN AND ABAMECTIN MO- © LECULES IN CAPSULE FORM

(57) Abstract: The present invention relates to a combination in capsule form comprising the molecules of bifenthrin and abamectin ¾ together, a method employed for preparing said capsule suspension formulation and use of said combination as a pesticide for the S control of harmful insects and red poultry mite and bird louse. A PESTICIDE COMPOSITION COMPRISING A COMBINATION OF BIFENTHRIN AND ABAMECTIN MOLECULES IN CAPSULE FORM

The present invention relates to a combination in microcapsule form comprising the molecules of bifenthrin and abamectin together, a method employed for preparing said capsule suspension formulation and use of said combination as a pesticide for the control of harmful insects and chicken mite and louse.

TECHNICAL FIELD

Pesticides are the substances or the substance mixtures, which are used in order to inhibit, control or reduce the damage of the pests. Pesticide may be a chemical substance, a biological agent such as virus or bacteria, an antimicrobial agent, a disinfectant or any other agent. Since most of the chemical pesticides are unable to exhibit an activity selective for the target organism, they may at the same time cause various side (adverse) effects on the organisms other than the targeted organism or even the death of the same. Many pesticides are also harmful for the human. They cause common diseases and undesirable problematic conditions in the humans as a result of the consumption of the living beings to which they are applied as a food by the humans.

Abamectin is a fermentation product belonging to the Avermectin group, which is a well known agricultural chemical in the industry. It is a compound, which is effective on many pests and which elicits the insecticide, nematicide and miticide characteristics. In the chemistry literature, abamectin is known with the CAS no.

71 751-41-2 as a mixture of

(10E, 14E, 16E)-(1R, 4S, 5 'S, 6S,6'R, 8R, 12S, 13S, 2OR, 21R,24S)-6'-[(S)-secondary-butylJ- 21, 24-dihydroxy-5 ',11,13, 22-tetramethyl-2-oxo-(3, 7,19 trioxatetracyclo[l 5.6. 1.14, 8.020,24] pentacosa-10,14,16,22-tetrain)-6-spiro-2'-(5',6'- dihydro-2'H-pyran)-12-yl 2, 6-dideoxy 4-0-(2, 6-dideoxy-3-0-methyl-a-L-arabino- hexapyranosyl)-3-0-methyl-a-L-arabino-hexapyranoside and (10E,1 4E, 16E)-

(1R, 4S, 5 'S, 6S, 6% 8R.12S, 13S, 20R, 21R, 24S)-21, 22-dihydroxy-6'-isopropyl-

5', 11, 13, 22-tetramethyl-2-oxo-(3, 7, 19-trioxatetracyclo

[15. 6.1. 14,8. 020,24]pentacosa-10,14,16,22-tetrain)-6-spiro-2'-(5', 6'-dihydro-2'H- pyran) 12-yl 2, 6-dideoxy-4-0-(2, 6-dideoxy-3-0-methyl-a-L-arabino-hexapyranosyl)- 3-O-methyl-a-L-arabino-hexapyranoside. Bifenthrin is a synthetic pyrethroid type insecticide effective against many agricultural pests. Bifenthrin molecule, having the chemical name 2-Methyl-3- phenylphenyl)methyl (IS,3S)-3-[(Z)-2-chloro-3,3,3-trifluoroprop-l -enyl]-2,2- dimethylcyclopropane-l-carboxylate, is known by the CAS no. 82657-04-3.

STATEOF THE ART

The pesticide manufacturers always search the ways for developing the pesticides in a way that is safer for the environment, humans and other non-targeted organisms and for formulating the same in a way that provides more effective and economical use against the targeted pests, or they receive the support from the academic institutions in this regard. The increasing environmental consciousness and the research conducted about the harmful effects of the chemicals have accelerated these efforts even further. Moreover, different combinations and different formulations are resorted to, in order to eliminate the situations such as the resistance to pesticides, which is acquired for various reasons. The harmful effects of the pesticides on the one hand and the health risks and economic losses caused by the insect pests on the other hand prompted the researches to seek a safer and more effective pesticide.

According to current practice, Bifenthrin and Abamectin molecules are used as formulations such as single suspension concentrates (SC), emulsion concentrates (EC), microcapsulation (CS, MC), water dispersible powder (WP), water dispersible granules ( DG, WG, SG), oil in water emulsions (EW), microemulsions (ME), oil based concentrates (ODC, OC, OD), etc. In this case, considerable resistance issues emerge with the continued applications of a pesticide molecule and as a result, the desired result may not be achieved. In addition, undue economic losses and environmental pollution occur.

The application no. WO20 12040802 discloses the concomitant use of the active ingredients of abamectin and bifenthrin. However, the use of said molecules in capsule suspension form and the unexpected benefits that could be obtained from such use are not mentioned. Further, said document does not mention the positive effect of the combination of abamectin and bifenthrin in the control of red poultry mite and bird louse.

Similarly, the application no. CN 130571 A discloses the combination of abamectin and bifenthrin and the use thereof as an insecticide. However, no specific dosage form is mentioned and no example is included to demonstrate the effects of said combination on various plant pests and the red poultry mite and bird louse.Although these two molecules were used together according to the prior art, the manufacture of a pesticide by the simultaneous use of these two molecules via the capsule suspension form was never attempted. The duration of the effect is short in the prior art; hence the expected insecticidal + acaricidal action has a short duration and it has been impossible to achieve the intended result in application. Moreover, the number of pests uncontrollable during the transition between the generations is at a level that may not be underestimated and it is not possible to achieve uninterrupted control over the insect pests.

Furthermore, the combinations of bifenthrin and abamectin, present in different forms according to the state of the art, have never achieved success in the control of red poultry mite (Dermanyssusgallined) in the veterinary hygiene or have never been tried for this purpose. The red poultry mite (Dermanyssusgallined) causes problem especially in the poultry sector for egg production.

Because the chicken mites can survive without feeding for about 6 months in the ambience where they are present, their control is generally very difficult. Besides, the winter seasons with mild weather conditions are very favorable for the survival and vitality of the mites.

Unlike the state of the art, the combinations comprising abamectin and bifenthrin that are used together in capsule form according to the present invention have been observed to provide great efficacy at low dose, exhibit insecticidal and acaricidal action against the insects damaging the agricultural products and achieve the successful results, which were not possible to obtain previously with any pesticide, in the control of the red poultry mite and bird louse.

OBJECT OF THE INVENTION

The object of the invention, realized based on the mentioned state of the art, is to combine the molecules of abamectin and bifenthrin by means of the capsule formulation technique, which formulation would eliminate the risks of insecticide resistance for the effective control of the insect pests posing a problem in the fields of agriculture and veterinary medicine (animal health - farm safety) and which would be capable of controlling more than one generation and different insect species by a single application.

With the invention, a novel means of solution is developed for the management of resistance, by way of combination of two different molecules with two different mechanism of action in a single formulation.

The object of the invention is to allow the development of the effective, ecological and economical compositions that achieve the ideal combination via ideal formulae.

Another object of the invention is to eliminate the irritation, enhance the activity and prolong the duration of action to advanced standards by way of capsulation of bifenthrin, a synthetic pyrethroid, and abamectin, a product belonging to the avermectin group, in a single combination.

With the invention, it is also intended to take more than one generation under control via single administration. This is achieved owing to the long duration of action of the invention.

Another object of the invention is to control multiple agricultural pests via single administration. The invention controls both the mites and the other insect pests.

Another object of the invention is to provide, via single administration, the possibility of effective control over the bunch moth (Lobesia spp.), which is a big problem in the vineyards, as well as enable the control of the red spider mites {Tetranychusurticae), which is also an important problem in the vineyards. In other words, it is intended to control two separate important pests by means of single administration.

Another object of the invention is to achieve success against the pear psilla. The administrations in Turkey against the pear psilla are performed at the dose of 1,8% Abamectin 65-75 cc/100 liter water. This administration achieves no result and the dose is increased by 2-3 folds due to the resistance. The increased dose is not sufficient either and various molecules are added by the farmer to the tank together with abamectin, in an unconscious manner. As a result, the pesticide residues develop on the fruit, the repeated application fails to yield satisfactory results after a certain period of time and the level of resistance becomes increasingly higher. Currently, the administrations in Turkey against this pest achieve no result with the exception of the administrations using the products that contain Spinetoram and Spirodiclofen. Of these molecules, the sensitivity has also emerged against Spirodiclofen, and therefore, the company Bayer has developed a novel product by the addition of abamectin to Spirodiclofen. On the other hand, Spinetoram has such an expensive price that prohibits the use of the same by the farmers. Owing to the invention, a novel economical means of solution is provided for the control of this pest, which has remained unresolved until now.

Another object of the invention is to control the red spider mite and codling moth, which are also the important pests of pear, by the action of the same administration against the pear psilla.

A novel object of the invention is to use the combination of abamectin and bifenthrin for the control of pistachio psilla (Agonoscenaspp.), as a practice never attempted before. For the control of this pest, the EC formulation of bifenthrin is employed, which is present as an ingredient of the combination of the prior art. In Turkey, 10% bifenthrin EC is registered and used at a dose of 20 cc/100 Liter water; however, this product is today unable to achieve any result at even a 3-fold higher dose (60 cc/100 Liter water). In addition to this product (Bifenthrin 10% EC), there is a great number of products containing different registered molecules, but none of these molecules proves effective at regular dose against the pest, due to resistance. Moreover, abamectin has never been tried previously for the control of said pest. The trial with the invention was conducted at a dose of 15-25 cc/100 liter water and a success in the range of 91-96% was achieved. The invention enabled the intended result to be achieved and thus achieved its goal.

By the invention, it is intended to control red spider mite (Tetranychus spp.) and other mites in the pome fruits and stone fruits other than the pear as well as controlling the codling moth (Cydiapomenalla) in the same fruits.

The invention also aims to provide the control of the red poultry mite (Dermanyssusgallinea) in the chicken. In the studies on the red poultry mite, many complex formulations such as alphacypermethrin + tetramethrin + PBO (SE, SC formulation), lambdacyhalothrin + chlorpyrifos (ZW formulation), permethrin + tetramethrin + PBO (EC, ME formulation), Spinosad (SC formulation), Matrin (AS formulation), etofenprox + tetramethrin + PBO (EC formulation), deltamethrin (SC formulation) were tried without any successful result. Following these studies, it was intended to control this pest with the invention and full control was achieved. Another object of the invention is to control, via single administration, the pests of white fly Be isiat b ci) and red spider mite (Tetranycus spp.), which cause a great extent of crop loss every year in the vegetables and cotton. This result stems from the combination of the insecticidal + acaricidal actions via the capsulation technique. Since the formulations prepared by the techniques other than capsulation would have a short time of action, no action may be observed that would extend to the emergence of another pest from a pest.

Still another object of the invention is to achieve effective result against the red spider mite, which is an important apple pest. This is an insect species, for which it is difficult to find solution due to its ability to rapidly develop resistance. Owing to the invention, an effective control power is provided for this pest, while at the same time controlling the codling moth, another apple pest, without having to perform a separate application.

Still another object of the invention is to achieve the control of different pests by single application. This is an advantage usually not much possible for the pests causing problems in different periods. By means of the capsulation technique for the combination of bifenthrin + abamectin, the action is enabled to be prolonged; hence the activity of the invention continues during the period when both the first emerging pests and the pests causing the density at a later stage are observed.

Still another object of the invention is both to enable economical control at lower dose and cause less environmental pollution.

Still another object of the invention is to obtain the barrier action that would prevent the ingress of the insect pests to the fields where the application is made.

Yet another object of the invention is to enable the prevention of the loss of insecticide/acaricide, which would result from the evaporation, owing to the use of the vapor retarder technology so that the product may be present for longer time in the target field.

Yet another object of the invention is to protect both molecules from sunlight and other external factors by way of keeping the same within the capsule.

In order to achieve the aforementioned objects, the development of the microcapsulation (CS, MC) of the synthetic pyrethroid insecticide + abamectin and the acaricide molecules belonging to the same group, which are used for the effective concomitant control of the insects and mites, is enabled.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the capsule forms simultaneously including the abamectin and bifenthrin molecules.

According to the invention, the simultaneous presence of the bifenthrin and abamectin molecules owing to the capsulation technique generates a synergistic action as well as allowing the insecticide and acaricide actions to be obtained via a single product and resulting in a controlled long-time activity.

Abamectin is a strong acaricide, but it is a molecule with poor insecticidal action. The duration of action for the abamectin molecule formulated other than the capsule form is limited to 5-7 days. Bifenthrin has strong insecticidal action, but it exhibits the character of a medium-strength acaricide. According to the invention, high insecticidal action as well as enhanced acaricidal action is achieved in a single combination. The studies demonstrating said action and the results of comparisons made with the existing formulations of the state of the art are presented to your attention in the examples.

By way of concomitant use of two molecules with different mechanisms of action (bifenthrin blocks the Na+ channels and abamectin is effective as an activator of chloride channels), in a capsulation formulation, the invention controls the insects resistant to bifenthrin group owing to the synergy of abamectin, while controlling the insects resistant to abamectin group owing to the synergy of bifenthrin. On the other hand, this action takes place via the capsule form. The other types of formulations have a short duration of action and the insect control remains limited to a part of the life phases of the insects. Since the capsule continuously releases these two active agents in the field of application, it controls both the young hatching individuals (larvae and nymphs) and the adult individuals, in other words, all the phases. The invention also exhibits activity to control the next 2-3 generations, thereby demonstrating an extraordinary biological activity. In short, the invention is a combination that adds a new dimension to the insect pest control against the problems frequently caused worldwide by the insects with and without resistance. With the formulations of the state of the art, new pesticide application is required against every generation of the pear psilla (Cacopsyllapyri), pistachio psilla (Agonoscena spp.), vegetable red spider mite (Tetranychusurticae), vineyard pests, especially the bunch moth (Lobesiabotrana), cotton green (Heliothis spp and pink bollworm (Pectinophora spp.), corn borer (Ostrinia spp.) and other plant pests in the spectrum, thus failing to enable an economical insect control due to the intensive labor involved and the great amount of pesticide used.

The invention optimizes the aforesaid benefit via the capsulation technique. With the applications involving the formulation techniques other than capsulation, the two molecules in free state will shortly disappear from the ambience due to the solar rays and other environmental factors (first abamectin, then bifenthrin). The shorter half- life of the abamectin molecule than bifenthrin will destroy the dual molecule action expected from the combination. The invention encapsulates both molecules, thereby preventing them from being affected by the solar rays and other environmental conditions and providing the possibility to obtain the desired action from both molecules in the pest control.

A feature of the invention is that the formulations according to the invention are used for the control of the plant pests. The invention provides the possibility of control over Lepidoptera, Arachnida, Hemiptera, Bilateria, Hymenoptera, Coleoptera, Diptera, Anoplura, Hymenoptera and all the other insect orders. Said plant pests may be the pear psilla (Cacopsyllapyri), pistachio psilla (Agonoscena spp.), vegetable red spider mite (Tetranychusurticae), vineyard pests, especially the bunch moth (Lobesiabotrana), cotton green (Heliothis spp.) and pink bollworm (Pectinophora spp), corn borer (Ostrinia spp.), vineyard bunch moth (Lobesia spp.), red spider mite (Tetranychusurticae), pome fruit and stone fruit codling moth (Cydiapomenalla), white fly (Bemisiatabaci), etc.

Due to the long duration of action and wide spectrum, the applications against the pear psilla, for example, may also enable the control over the pear codling moth and pear red spider mite by the action of the single administration.

In another aspect, the present invention relates to the use of the formulation according to the invention, which comprises together the abamectin and bifenthrin molecules in a capsule formulation, for the control of chicken mite and red louse. The invention was tested on the red poultry mite (Dermanyssusgallinea), a great problem worldwide, and surprisingly successful results were obtained, which had not been possible to achieve with any pesticide previously.

Another feature of the invention is that the abamectin and bifenthrin molecules exhibit synergistic action, thus providing greater effect at lower dose. The formulation according to the invention comprises abamectin at a ratio of 0,001-35% by weight, preferably 0,1 - 10% by weight, particularly preferably 0,5-5% by weight, whereas it comprises bifenthrin at a ratio of 0,01-55% by weight, preferably 0,1-40% by weight, particularly preferably 0,5-25% by weight. According to a preferred embodiment of the invention, abamectin is used at a ratio of 3.6% by weight and bifenthrin is used at a ratio of 10% by weight.

As a particular alternative to bifenthrin employed in the invention, it would be possible to use the following: Acrinathrin, bioresmethrin, cyfenothrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyclothrin, lambda-cyclothrin, gamma-cyclothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, teta-cypermethrin, zeta- cypermethrin, deltamethrin, empenthrin, [(EZ)- (1R)- isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, permethrin, fenothrin [(lR)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tralomethrin and other synthetic pyrethroids and acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorphenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imisiaphos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isozathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenophos, propetamphos, protiophos, pyraclophos, pyridafenthion, quinalphos, sulfotep, tebupyrimphos, temephos, terbuphos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion and chlordane, endosulfan and other organaphosphorous substances as well as ethiprole and fipronil of phenylpyrazole (Fiproles) group and indoxycarb of the indoxacarb group. These alternatives would also be used at the same weight ratios as bifenthrin, i.e. at amounts corresponding to the weight ratios in the range of 0,01-55%.

As a particular alternative to abamectin, it would be possible to use the following insecticides/acaricides in the invention: Emamectin benzoate, lepimectin, milbemectin, azadirachtin, clofentezine, hexathiazox, diflovidazin, Tetronic and Tetramic acid derivatives such as spirodiclofen, spiromesiphen, spirotetramate, plant extracts such as oxymatrine. These alternatives would also be used at the same weight ratios as abamectin, i.e. at amounts corresponding to the weight ratios in the range of 0,001-35%.

The common alternatives for bifenthrin and abamectin are the substances from the group of neonicotinoids such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam and the spinetoram and spinosad molecules from the group of spinosyns. Any one of these common alternatives would be used only once in the combination as an alternative for bifenthrin or abamectin.

One of the common alternatives may be used in place of any one of the abamectin or bifenthrin molecules or in place of a molecule indicated as a particular alternative for these molecules. For example, a formulation according to the invention may be as follows: Abamectin (or particulate alternatives thereof) + dinotefuran (or bifenthrin alternatives or other common alternatives). Both molecules may not be used alternatively at the same time in the formulation. The same molecule among the common alternatives may not be used for the second time as an alternative both for abamectin and bifenthrin. For example, the use of imidacloprid (common alternative for bifenthrin) + imidacloprid (common alternative for abamectin) is out of the scope and this is already a mixture that is not a combination. Moreover, of these alternatives that belong to the same group, the use of one in place of bifenthrin and of another in place of abamectin is not possible. Example: The combination of acetamiprid + dinotefuran would not be an alternative. The use of different groups would also be considered among the alternatives. For example, a combination such as acetamiprid + spinosad could be a combination according to the invention.

If the common alternative is to be used in place of bifenthrin, its weight ratio would be in the range of 0,01-55%, and if the common alternative is to be used in place of abamectin, its weight ratio would be in the range of 0,001-35%. All the active ingredient combinations mentioned above, their formulations in capsule suspension form, the methods for preparing the same in capsule suspension form and the use of the same in combined form and in capsule suspension form for the control of plant pests, red poultry mite and louse are encompassed by the invention. The formulations for said combinations, the methods for preparing these formulations and their fields of use are as described for the combination of abamectin and bifenthrin in the present specification and claims. Said combinations exhibit unexpected positive effect in the control of plant pests and red poultry mite and bird louse, just like the abamectin and bifenthrin combination. The combination of abamectin and bifenthrin according to the present invention may also include some auxiliary substances in addition to these active agents. Said auxiliary substances may be selected from solvents, antimicrobial preservative agents, emulsifiers, anti-foam agents, anti-freezing agents, at least 3 reactants, thickener and carrier.

According to a preferred embodiment of the invention, an auxiliary substance group comprising the solvent, emulsifier mixture, antimicrobial preservative agent, anti- foam agent, anti-freezing agent, 3 reactants, thickener and carrier is used.

The above-mentioned emulsifier mixture may be in the form of a composition of more than one emulsifier or a single emulsifier. The emulsifier(s) may be from ionic, anionic and nonionic groups or they may also be a combination of these groups. The emulsifiers able to be used in the product may be selected from a group comprising aminethoxylates, EO/PO block polymers, ether sulfates, saturated alcohol alkoxylates, saturated alcohol ethoxylates, sorbitan ester ethoxylates, tributylphenolethoxylates, phosphate esters, tristyrylphenolethoxylates, sulfonation products, polycondensation products, nonyl phenol ethoxylates, alkyl benzene sulphonates, castor oil ethoxylates, EO/PO alkoxylation products, saturated alcohol ethoxylates, olein sulphonates and sulfosuccinate groups or a combination thereof. In other words, the emulsifying agents mentioned above may be used alone or they may be used in combinations according to various proportions. In the formulation, tristyryl phenol ethoxylate and phosphate nonyl phenol ethoxylate groups are preferably used and a 1/1 mixture of the tristyryl phenol ethoxylate and phosphate nonyl phenol ethoxylate groups is particularly preferred. The solvent mentioned above is the liquid medium in which the normally solid abamectin and bifenthrin active ingredients are dissolved. Since the invention is realized by means of the interface polymerization technique, it may be formulated using only the water-insoluble solvents. For this purpose, said solvent may be selected from the group comprising the hydrocarbons such as xylene, benzene, toluene, cyclohexane, cyclohexanone, solvesso 100, solvesso 150, solvesso 200 and exxsol series as well as the vegetable oils obtained from the oily seeds, ethyl and methyl esters thereof, alcohols, glycols, acetates, ketones, amides, amines, saturated and unsaturated hydrocarbons, acid esters and the terpenes of the plant origin. A combination of more than one solvent may be used instead of only one solvent. Xylene is used as the preferred solvent in the formulation of the combination according to the present invention. The solvent is used in said formulation at a ratio of 0,5-70% by weight, preferably 5-50% by weight, particularly preferably 10-40% by weight.

The anti-freezing agent mentioned in the table is a glycol derivative additive that prevents freezing at low temperatures as a known practice in the water-based pesticide formulations. These additives are selected from a group comprising ethylene glycol, monopropylene glycol, dipropylene glycol, diethyleneglycol and glycerin. Monopropylene glycol is preferably used in formulating the combination according to the present invention. In said formulation, the anti-freezing agent is used at a ratio of 0,00 1-30% by weight, preferably 0,1-20% by weight, particularly preferably 1-10% by weight.

1 of the 3 reactants mentioned in the table (Reactant 1) is selected from the organic compounds that contain isocyanate functional group. The function of this reactant in the formulation is to enable, after the formation of the emulsion by the addition of the prepared insecticide molecules into the oil phase, the polymerization on the emulsion droplets-water interface with the aid of the catalyst solution and the formation of the polyurea capsule wall. Reactant 1 is selected from the group comprising methyl isocyanate, methylene diphenyldiisocyanate (MDI), hexamethylenediisocyanate (HDI), toluenediisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexylisocyanate (HMDI) or isophoronediisocyanate (IPDI).

The other reactants mentioned above (Reactant 2 and Reactant 3) are the amines, which undergo polymerization reaction with Reactant 1, belonging to isocyanate group, and form a polyurea capsule shell. The preliminary mixture of Reactant 2 and Reactant 3 is prepared in water to produce the catalyst solution. The prepared catalyst solution is slowly added on the oil phase of the insecticide molecules emulsified in water, thereby initiating the reaction for the formation of the polyurea capsule shell. The amines used in the synthesis of the polyurea capsule shell may belong to the primary, secondary or tertiary amine groups. Said amines encompass ethylamine, ethylene diamine, diethylenetriamine, triethylenetetraamine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine.

In said formulation, Reactant 1 is used at a ratio of 0,001-40% by weight, preferably 0,1-20% by weight, particularly preferably 1-10% by weight.

In said formulation, Reactant 2 is used at a ratio of 0,001-40 by weight, preferably 0,1-20% by weight, particularly preferably 1-10% by weight.

In said formulation, Reactant 3 is used at a ratio of 0,001-50% by weight, preferably 0,1-20% by weight, particularly preferably 0,5-10% by weight.

The thickener mentioned above means the additives that may be used in order to adjust the viscosity of the formulation once the polymerization reaction is over. These include xanthan gum, guar gum, gum arabic, carboxymethyl cellulose, methyl cellulose, hydroxypropylcellulose. Xanthan gum is preferably used in the formulation.

In said formulation, the thickener is used at a ratio of 0,0001-30% by weight, preferably 0,01-20% by weight, particularly preferably 0,01-10% by weight.

The above-mentioned carrier is water and the anti-foaming agent and the antimicrobial preservative agent are the products frequently used in the pesticide formulations. In the formulation, the silicone-based anti-foaming agent is preferably used. The carrier is used at a quantity sufficient to complement the amounts of other auxiliary agents to 100%.

The combination of abamectin and bifenthrin according to the present invention is preferably in capsule form. However, the administration of the combination of the active ingredients of abamectin and bifenthrin in alternative liquid or solid formulations via certain techniques of application is also included in the scope. Said solid formulation may be water dispersible powder (WP), water dispersible granules (WDG), water soluble granules (SG). Likewise, said liquid formulation may be emulsifiable concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), oil in water emulsion (EW), nano capsules (NC) as well as controlled release microcapsules (CS) or a mixture (ZC, ZW, ZE) of the capsule formulations with EC, EW, SE, SC.

The methods of manufacture for the formulations other than the capsule suspension (CS) are similar to or same as the current (known) technique for said formulations. Said formulations relate to the concomitant formulation of the molecules of abamectin + bifenthrin or their alternatives for the use of the same in the control of plant pests and chicken mites.

The type of formulation preferred according to the invention is the capsule suspension (CS) that performs controlled release from liquid formulations. The microencapsulation of the active ingredients may be carried out via the methods known in the art in order to achieve the synergistic action, render the formulation safer bearing the irritating effects of the active ingredients in mind and prolong the duration of action.

Another aspect of the present invention relates to a method for the manufacture of a capsule formulation of bifenthrin and abamectin molecules.

Said method comprises the following steps:

- Abamectin and bifenthrin are mixed with the solvent and capsule reactant 1 to prepare an emulsifiable formulation of abamectin and bifenthrin; - Emulsifier or emulsifier mixture, anti-freezing agent, antimicrobial preservative agent and anti-foam agent are added to the water to prepare the water phase of the emulsion; - The prepared solution of abamectin and bifenthrin is emulsified in water phase by means of a high-speed mixer, - Aqueous solution of reactant 2 and reactant 3 is slowly added into the formed emulsion to initiate the reaction for the formation of the polyurea capsule shell; - The mixture is allowed to stand for the completion of the initiated polymerization reaction; - The viscosity is adjusted with the aid of the thickener. The examples disclosing the present invention and the results of comparisons with the state of the art are presented to your attention in the following section of examples.

EXAMPLES

Example 1: Comparison of the combination according to the invention with the formulations existing in the state of the art

The results of the experiments, which show the effects of the formulation prepared according to the present invention and the formulations existing in the state of the art on various plant pests, are presented in the table below: CS

As can be seen from the results in the table provided above, the formulation 4 and 5, which contain the molecules of abamectin and bifenthrin in combined form (Bifenthrin 12% + Abamectin 4% EC and Bifenthrin 10% + Abamectin 3,6% CS), exhibit longer duration of action as compared to the formulation 1, 2 and 3, in which said active ingredients are used alone. When the formulations that use the molecules of abamectin and bifenthrin in combined form and that differ in terms of dosage form are examined, the formulation 4 in EC form is observed to contain greater amounts of abamectin and bifenthrin, require the use at greater quantity and exhibit shorter duration of action. As evident from this example, the use of the abamectin and bifenthrin combination according to the invention in capsule form, unlike the state of the art, enables the use of less active ingredient, allows greater efficacy to be obtained at lower doses and exhibits a duration of action that is up to 2-3 times longer than that of the different form (EC) of the same combination. Longer duration of action also prevents the escape of the pests at the transition between the generations.

When the results in the table given above are considered:

1. The present invention made it possible to widen the pesticide spectrum. The widening of the spectrum allows the control of more than one pest by a single application. For example, by means of the application against the pear psilla, the control of pear red spider mite and codling moth is also provided. This provides the possibility of more effective control with less labor and less amount of product. Moreover, a complex mechanism of action was achieved, which enabled both insecticidal and acaricidal action to be improved. A good alternative product was obtained also for the resistance management.

2. The present invention provided the possibility of greater control at low dose.

3. The present invention prolonged the duration of action for the product. This result was achieved owing to the special capsulation formulation technique.

Although the EC combination (formulation 4) enables to obtain the widening of the spectrum among these advantages of the invention, this formulation fails to offer the advantages in items 2 and 3 above.

Example 2: Comparison of the efficacy of the combination according to the invention with that of the combination of the separately capsulated active ingredients The inventors separately capsulated the molecules of abamectin and bifenthrin via the method disclosed within the scope of the invention and brought these together via the method of mixing in the tank of the pesticide application device (test mixture). The efficacy of this product obtained in combined form was assessed and the obtained results were compared to that for the formulations in which the molecules of abamectin and bifenthrin were capsulated together according to the invention. As a result, the test mixture was observed to have, upon 9 repetitions, a success ratio in the range of 43 - 65% against the pests. When the test was conducted on the same pests using the formulation according to the invention, a success rate of at least 90% was observed.

Example 3: Demonstration of the effect of the combination according to the invention on the red poultry mite

In July 2014, the tests were conducted in the poultry house with the most severe problem of chicken mite, belonging to Bozoklar Poultry in the province of Bahkesir. The tests were performed between 21.00-23.00, which is the period when the mites are most active and most frequently observed. Results:

1. During the night time application, the population of flies (Musca spp.), another insect pest, was observed to be very high in the poultry house. During the application, the fly population was observed to disappear. This indicates that the invention also solves the problem of flies, which is also significant in the farms, in addition to the chicken mite, the primary target of the invention.

2. At the checks performed 12, 36 and 72 hours after the application in the farm, no chicken mite was found. During the checks on day 14, the chickens were taken out of the poultry house. This was expected to cause the emergence of a greater number of surviving mites. However, this check revealed neither surviving mites nor flies. During the checks on day 21, the efficacy was observed to be preserved without any reduction.

The control of mites is a rather difficult issue due to both the biological characteristics and life ecology of the mites. With the addition of the resistance problem to these, the mites became a problem that is very hard to solve all around the world. The invention will have a more special place than the prior art, as an important means of solution that eliminates this problem. Example 4: The formulation accordins to the invention and the method for preparing the formulation

The capsule formulation according to the invention is obtained by combining the ingredients with % ratios by weight given above, via the method described below. (The other known capsulation manufacturing techniques for obtaining the capsulation combination of bifenthrin + abamectin are also included in the scope.)

Manufacturing Method:

i. Abamectin and bifenthrin are mixed with the solvent and capsule reactant 1 to prepare an emulsifiable formulation of abamectin and bifenthrin; ii. Emulsifier or emulsifier mixture, anti-freezing agent, antimicrobial preservative agent and anti-foam agent are added to the water to prepare the water phase of the emulsion; iii. The prepared solution of abamectin and bifenthrin is emulsified in water phase by means of a high-speed mixer; iv. Aqueous solution of reactant 2 and reactant 3 is slowly added into the formed emulsion to initiate the reaction for the formation of the polyurea capsule shell; The mixture is allowed to stand for the completion of the initiated polymerization reaction; The viscosity is adjusted with the aid of the thickener. CLAIMS

1. A formulation simultaneously comprising the molecules of abamectin and bifenthrin characterized in that it is in capsule suspension form. 2. A formulation according to Claim 1 characterized in that it comprises 0,001-35% by weight abamectin and 0,01-55% by weight bifenthrin. 3. A formulation according to Claims 1 and 2 characterized in that it comprises 3.6% by weight abamectin and 10% by weight bifenthrin. 4. A formulation according to Claims 1-3 characterized in that in addition to the active ingredients of abamectin and bifenthrin, it comprises at least one auxiliary substance selected from the solvents, antimicrobial preservative agents, emulsifier, anti-foam agent, anti-freezing agent, at least 3 reactants, thickener and carrier. 5. A formulation according to Claim 4 characterized in that the emulsifier is selected from a group comprising aminethoxylates, EO PO block polymers, ether sulfates, saturated alcohol alkoxylates, saturated alcohol ethoxylates, sorbitan ester ethoxylates, tributylphenolethoxylates, phosphate esters, tristyrylphenolethoxylates, sulfonation products, polycondensation products, nonyl phenol ethoxylates, alkyl benzene sulphonates, castor oil ethoxylates, EO/PO alkoxylation products, saturated alcohol ethoxylates, olein sulphonates and sulfosuccinate groups or a combination thereof. 6. A formulation according to Claims 4-5 characterized in that tristyryl phenol ethoxylate and phosphate nonyl phenol ethoxylate are used as the emulsifier. 7. A formulation according to Claim 6 characterized in that a 1/1 mixture of tristyryl phenol ethoxylate and phosphate nonyl phenol ethoxylate groups is used. 8. A formulation according to Claims 4-7 characterized in that the solvent is a water- insoluble solvent. 9. A formulation according to Claims 4-8 characterized in that the solvent is selected from a group comprising the hydrocarbons such as xylene, benzene, toluene, cyclohexane, cyclohexanone, solvesso 100, solvesso 150, solvesso 200 and exxsol series as well as the vegetable oils obtained from the oily seeds, ethyl and methyl esters thereof, alcohols, glycols, acetates, ketones, amides, amines, saturated and unsaturated hydrocarbons, acid esters and the terpenes of the plant origin. 10. A formulation according to Claims 4-9 characterized in that it comprises the solvent at a ratio of 0,5-70% by weight.

1. A formulation according to Claims 4-10 characterized in that the anti-freezing agent is selected from a group comprising ethylene glycol, monopropylene glycol, dipropylene glycol, diethyleneglycol and glycerin.

12. A formulation according to Claim 1 1 wherein monopropylene glycol is used as the anti-freezing agent. 13. A formulation according to Claims 4-12 wherein the anti-freezing agent is used at a ratio of 0,001-30% by weight. 14. A formulation according to Claims 4-13 wherein one of the 3 reactants used (Reactant 1) is selected from a group comprising methyl isocyanate, methylene diphenyldiisocyanate ( DI), hexamethylenediisocyanate (HDI), toluenediisocyanate (TDI), naphthalene diisocyanate (NDI), methylene bicyclohexylisocyanate (HMDI) or isophoronediisocyanate (IPDI). 15. A formulation according to Claims 4-14 wherein two of the 3 reactants used (Reactant 2 and Reactant 3) are selected from a group comprising ethylamine, ethylene diamine, diethylenetriamine, triethylenetetraamine, dimethylamine, trimethylamine, diethylamine, diisopropylamine, dimethylaminopropylamine, triisopropylamine . 16. A formulation according to Claims 4-15 wherein the reactant 1 is used at a quantity of 0,001-40% by weight. 17. A formulation according to Claims 4-16 wherein the reactant 2 and reactant 3 are used at quantities of 0,001-40% and 0,001-50% by weight, respectively. 18. A formulation according to Claims 1-17 characterized in that it comprises 0,001- 35% by weight abamectin, 0,01-55% by weight bifenthrin, 0,5-70% by weight solvent, 0,001-50% by weight antimicrobial preservative agent, 0,001-50% by weight anti-foam agent, 0,001-30% by weight anti-freezing agent, 0,001-40% by weight reactant 1, 0,001-40% by weight reactant 2, 0,001-30% by weight reactant 3, 0,0001-30% by weight thickener and optionally the carrier. . A formulation according to Claims 1-18 characterized in that it comprises 3,6% by weight abamectin, 10% by weight bifenthrin, 22% by weight solvent, 0,3% by weight antimicrobial preservative agent, 1% by weight anti-foam agent, 4% by

weight anti-freezing agent, 5% by weight reactant 1, 2% by weight reactant 2, 1% by weight reactant 3, 0.08% by weight thickener and optionally the carrier. 20. A formulation simultaneously comprising the molecules of abamectin and bifenthrin characterized in that it is manufactured via the capsulation technique. 21. A formulation according to Claim 20 characterized in that it is manufactured by a production method comprising the steps of i. mixing abamectin and bifenthrin are with the solvent and capsule reactant 1 to prepare an emulsifiable formulation of abamectin and bifenthrin; ii. adding emulsifier or emulsifier mixture, anti-freezing agent, antimicrobial preservative agent and anti-foam agent to the water to prepare the water phase of the emulsion; iii. emulsifying the prepared solution of abamectin and bifenthrin in water phase by means of a high-speed mixer; iv. slowly adding the aqueous solution of reactant 2 and reactant 3 into the formed emulsion to initiate the reaction for the formation of the polyurea capsule shell; v. allowing the mixture to stand for the completion of the initiated polymerization reaction; vi. adjusting the viscosity with the aid of the thickener. 22. A manufacturing method according to Claims 20 and 2 1 characterized in that in step iv, the aqueous solution of reactant 2 and reactant 3 is slowly added on the oil phase of the abamectin and bifenthrin molecules emulsified in water, thereby initiating the formation of the polyurea capsule shell. 23. Use of the formulation according to Claims 1-19 for the control of red poultry mite and bird louse. 24. Use of a formulation according to Claims 1-19 for the control of Lepidoptera, Arachnida, Hemiptera, Bilateria, Hymenoptera, Coleoptera, Diptera, Anoplura, Hymenoptera and other insect orders. 25. Use of a formulation according to Claims 1-19 for the control of the pear psilla (Cacopsyllapyri), pistachio psilla (Agonoscena spp.), vegetable red spider mite (Tetranychusurticae), vineyard pests, especially the bunch moth (Lobesiabotrana), cotton green (Heliothis spp.) and pink bollworm (Pectinophora spp.), corn borer {Ostrinia spp.), vineyard bunch moth (Lobesia spp.), red spider mite (Tetranychusurticae), pome fruit and stone fruit codling moth (Cydiapomenalla), white fly (Bemisiatabaci). 26. A method for use in the manufacture of a formulation according to Claims 1-19 characterized in that it comprises the steps of i. mixing abamectin and bifenthrin are with the solvent and capsule reactant 1 to prepare an emulsifiable formulation of abamectin and bifenthrin; ii. adding emulsifier or emulsifier mixture, anti-freezing agent, antimicrobial preservative agent and anti-foam agent to the water to prepare the water phase of the emulsion; iii. emulsifying the prepared solution of abamectin and bifenthrin in water phase by means of a high-speed mixer; iv. slowly adding the aqueous solution of reactant 2 and reactant 3 into the formed emulsion to initiate the reaction for the formation of the polyurea capsule shell; v. allowing the mixture to stand for the completion of the initiated polymerization reaction; vi. adjusting the viscosity with the aid of the thickener. INTERNATIONAL SEARCH REPORT

PCT/TR2O15/O0O350

I NV . A91 P7/0O A0 1P7/02 A 1P7/04 AO1P5/O0 A01N25/28 A01N25/O4 A 1N43/90 A01N53/O6 ADD .

A01N

EPO- I nternal WPI Data , CH E ABS Data

WO 2 11/015220 Al (GAT I CRO ENCAPSU LATI ON 1-26 AG [AT] ; CASANA GI NER VI CTOR [AT] ; GI MENO SI ERR) 1 February 201 1 ( 201 1-02 - 10) c l a i ms 1-22 page 7 , 1i ne 29 ; c l a i m 23 exampl e s 5 . B - 5 . D

CN 1 3 004 858 A ( LI J I ANZH0NG) 1-26 3 Apri l 2013 ( 2013 - 4 - 3 ) the whol e document

W0 2014/009269 Al ( ENDU RA SPA [ I T] ) 1-26 16 January 20 14 ( 2014-01 - 16) c l a i ms 1-31

-/--

X I

18 February 2016 16/03/2016

Kamdzh l v Yavor INTERNATIONAL SEARCH REPORT International application No PCT/TR2O15/O0O35O

C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category" Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

WO 2012/040802 A2 ( FMC QU I MI CA DO BRAS I L 1-25 LTDA [BR] ; BO RGES L U I S DONZ I ETE [BR] ; FABRI CARL) 5 Apri l 2012 (20 12 -04 -05 ) c i ted i n the appl i cati on the whol e document INTERNATIONAL SEARCH REPORT International application No Information on patent Tamlly members PCT/TR2O15/O0O350

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

WO 2011015220 A l 10-02-2011 AR 080604 A l 25-04-2012 CN 102548413 A 04-07-2012 EP 2461689 A l 13-06-2012 US 2012220456 A l 30-08-2012 US 2014010854 A l 09-01-2014 WO 2011015220 A l 10-02-2011

CN 103004858 A 03-04-2013 NONE

W0 2014009269 A l 16-01-2014 AU 2013289339 A l 22-01-2015 EP 2871952 A l 20-05-2015 US 2015237861 A l 27-08-2015 wo 2014009269 A l 16-01-2014

W0 2012040802 A2 05-04-2012 AR 083215 A l 06-02-2013 BR P I 1003434 A2 22-01-2013 UY 33633 A 30-04-2012 WO 2012040802 A2 05-04-2012