WO2012040803A2

WO2012040803A2 - Synergetic combination of imidacloprid and bifenthrin, its process of formation and uses and method of use

Info

Publication number: WO2012040803A2
Application number: PCT/BR2011/000345
Authority: WO
Inventors: Luis Donizete Borges; Leandro Anderlin Garcia; Carlos Eduardo Fabri; Antonio Moreira Lima; Roberta De Fatima De Godoy; Ricardo Werlang Camara
Original assignee: Fmc Química Do Brasil Ltda
Priority date: 2010-09-29
Filing date: 2011-09-26
Publication date: 2012-04-05
Also published as: WO2012040803A3; AR083216A1; WO2012040803A8; BRPI1003430A2; UY33636A

Abstract

The present invention refers to an agrochemically synergistic formulation imidacloprid and bifenthrin, in specific ratios to control and/or combat pest and diseases in crops. Are also described their process of preparation, use and method of use and the use of imidacloprid and bifenthrin in preparation of agrochemically synergistic formulation of the invention.

Description

Title: "SYNERGETIC COMBINATION OF IMIDACLOPRID AND BIFENTHRIN, ITS PROCESS OF FORMATION AND USES AND METHOD OF USE".

BACKGROUND OF THE INVENTION

The present invention refers to the synergetic combination of active ingredients imidacloprid and bifenthrin to control pests in soybean, cotton, beans, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn cultures.

Imidacloprid is an insecticide known to control a variety of pests. US Patent 4.742.060 provides a description of imidacloprid and some of its uses. Imidacloprid propitiates some control of hemiptera insects of the Aphididade family, mainly those popularly known as aphids. However, many other pests are part of the complex of pests of major such as soybean, cotton, beans, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn.

Bifenthrin is an insecticide known for controlling a variety of pests. US Patent 4.238.505 propitiates a description of bifenthrin and some of its uses. Generally, bifenthrin is known as 2-methylbiphenyl-3 ilmethyl (z)- (1 RS,3RS)-3-(2-cloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropane- carboxilate, registration number CAS 82657-04-3. Bifenthrin is described in The Pesticide Manual, page 88 (entry 76), C.D.S. Thomas, 13^rd edition, 2003. Bifenthrin is known for offering some control of lepiteropteran insects of the Noctuidae family, mainly those popularly known as caterpillars.

This invention can be used to control the following pests, in the following crops:

Soybean crop: Euchistus herus, Nezara viridula, Piezodorus guidini, Dichelops furcatus, Edessa meditabunda Anticarsia gemmatalis and Pseudoplusia includens, Tetranichus urticae and Polyphagotersunemus latus.

Cotton crop: Anthonomus grandis, Alabama argilacea, Pseudoplusia includens, Spodoptera eridanea, Pectinophora gossipiela.

Beans crop: Euchistus herus, Nezara viridula, Piezodorus guidini, Diabrotica speciosa, Empoaska kraemeri, Bemisia tabaci and Pseudoplusia includes.

Wheat crop: Pseudaletia sequax and Dichelops furcatus, Rhopalosiphum graminum.

Potato crop: Lyriomyza huidobrensis, Thripes palmi, Phthorimaea operculella.

Tomato crop: Lyriomyza trifolii, Thripes palmi.

Among pests mentioned above, we can highlight the bed bug Euchistus heros, which is a phytophagous bed bug considered one of the main pest insects attacking soybean crops in Brazil. Its damages are caused by the introduction of its mouth apparatus in developing grains or seeds, which harms tissues and causes serious damages regarding the allowance and quality of seeds, resulting in low strength and low tenor of oil in seeds, and propitiates the entry of fungi, which might cause other diseases to plants.

According to researchers Paulo Degrande and Lucia Vivan (Cultivar Magazine, 2008), when bed bugs attack pods, losses reach high levels, even higher than 30%. If the attack happens during the formation of grains, grains will shrink and be spotted, of lesser value due to the reduction in their tenor in oil. In this case, losses of seed germinating power can be of 50%.

In short, bed bugs cause losses to soybean due to reduction of productivity, through effects over pods and/or grains, reductions in germinative power and seed strength, reduction of tenors in proteins and oil in grains, and inoculation of pathogenic elements in the seed.

SUMMARY OF THE INVENTION

The main objective of this invention is to propitiate a specific synergetic combination (pre-mix) of bifenthrin + imidadoprid, coded as "BF 404-06", in order to control a broader spectrum of pests in soybean, cotton, beans, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn cultures.

Another objective of the invention is to reduce the quantity of active ingredient per hectare, because the synergy of the molecules of invention BF 404-06 (bifenthrin + imidadoprid) propitiates applications with lesser quantities of active ingredient per ha of imidadoprid. Another important and unexpected technical factor that has been observed by the inventors is related to the increase in the residual insecticide effect of product BF 404-06 when compared to bifenthrin applied alone. This longer effect reduces the number of applications to control the insect, and reduces the cost/ha for the producer.

The present invention, besides offering all synergetic benefits of the pre-mix to control pests, doesn't cause an unbalance of mites, which always happens whenever other pyrethorids are applied. According to Valentini et al. (1980), the mite is resistant to pyrethroids, and the use of this kind of product irritates females, provokes their dissemination, stimulates oviposition and eliminates natural enemies like thysanoptera, ladybugs, crisopidae and bed bugs.

The invention BF 404-06 (bifenthrin + imidacloprid) is an important tool to handle the resistance of pests to insecticides, as a mix of two active ingredients from different chemical groups.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a solid or liquid formulation. Under the solid form, it should be used as wettable powder (Po-Molhavel - PM) and/or Water Dispersible Granules (WDG), and under the liquid form, it should be used as an Emulsifiable Concentrate (EC), concentrated suspention (CS), Suspoemusion (SE) and/or concentrated emulsion (EW), but preferably as SC, not excluding other types of formulation.

The ratio between the quantity of imidacloprid and the quantity of bifenthrin is of around 8-12 parts of imidacloprid to around 1-5 parts of bifenthrin. A particularity of the invention is that the ideal ratio imidacloprid: bifenthrin is around 10:3.

With formulations of 1 L, the concentration in gia/L (gia = grama de ingrediente ativo - grams of active ingredient) of bifenthrin is of around 1 to each 699gia/L, and regarding imidacloprid, it is around 699 to around 1 gia/L. Preferably, the concentration of bifenthrin is around 30gia/L, and for imidacloprid, it is around 100gia/L. The concentration of the sum of active ingredients in final formulation might normally vary from about 10gia/L to about 700gia/L, preferably around 300gia/L.

The rest of a formulation of up to 1 (one) liter can include suitable vehicles, additives and/or excipients, which can be selected among water, surfactants, anti-foaming agents, anti-freezers, rheology modifiers, dispersants, wetting agents, bactericides or bacteriostatic agents, dyes, antiagglomerating agents and stabilizing agents, and their mixes.

The vehicle might normally be inert, made of organic or inorganic material, natural or synthetic. The vehicle, if solid, could be clay, silicates, silica, resins, waxes, cellulose fibers, fertilizers or alike, and might be used alone or together. If liquid, the vehicle could be water, alcohols from C1 to C14 chains, glycols, acetates, ketones, glycerids, saturated or unsaturated hydrocarbons, fatty acid esters, vegetable oils, mineral oils, or similar, and might be used alone or together. Preferably, water is used as vehicle.

Surfactants can be of ionic, non-ionic, cationic or polymeric type. Anionic surfactants that can be used in this invention could be: dodecylbenzene sulphonic acid, linear or branched, under the acid or neutralized form, nitrogenous derivates, sulfonated aromatic polymers under the acid or neutralized form, sulphonated naphthalene formaldehydes under the acid or neutralized form, condensed or not, lignosulfonates. Being these, preferably, sulphated and/or sulfonated surfactants.

Non-ionic surfactants that can be used in this invention could be: alkoxylates like alkoxylated sorbitan esters, alkoxylated alcohols, alkoxylated vegetable oils, alkoxylated fatty acids, among others; fatty esters like polyethylene glycol esters, glycerol or polyglycerol esters, sorbitan esters; amides like fatty amide of ethanolamine or ethylene amines, fatty imidazolines, among others. Preferably, alkoxylated alcohols with capric, caprylic, isodecylic, isotridecylic, decylic, lauric, stearylic, oleic, nonyl phenylic chains, with alkoxylation degree of 1 to 16 mols of ethene oxide and/or propene oxide, are used; alkoxylated vegetable oils like alkoxylated castor bean oil with alkoxylation degree between 5 and 54 mols of ethene oxide or propene oxide; alkoxylated sorbitan esters with alkoxylation degree between 5 and 80 mols of ethene oxide and/or propene oxide. Cationic surfactants that can be used in this invention are alkyl trimethyl ammonium hydrochlorides, dialkyl dimethyl ammonium hydrochloride, alkyl hydroxyethyl dimethyl ammonium hydrochloride, cetyl trimethyl ammonium hydrochloride, distearyl dimethyl ammonium hydrochloride, quaternary esters, among others.

Polymeric surfactants that can be used in this invention are ethene oxide and propene oxide block copolymers, mainly those with butylic chain, polyacrylate copolymers, methyl methacrylate copolymers, among others.

This invention also relates to a process to prepare its formulations, as for instance the Concentrated Suspension formulation, which comprises the following steps:

Water, surfactants and additives are mixed in a recipient; To the mixture add the bifenthrin in the molten form, were it remais agitated suffering a process of recrystallization;

After the recrystallization process is concluded, Imidacloprid is added

After all raw materials have been added, the formulation undergoes a grinding process, in which there will be more interaction among molecules and reduction of active ingredients particle size, thus increasing the synergism between molecules and their efficacy in the field.

After being grinded, the formulation undergoes a process of deaeration and densification to increase its physical stability, then obtaining a stable and synergetic agrochemical formulation.

- Then, it is bottled in high density polyethylene bottles/jerricans and distributed in the market.

Another possibility of the invention is to use imidacloprid and bifenthrin in the preparation of formulations to control and/or combat pests and diseases in vegetable crops.

The invention also includes the use of formulations to control and/or combat pests and diseases in vegetable crops.

Another possibility of the invention is a method to control and/or combat pests and diseases in vegetable crops, which includes de application of formulations to the mentioned pests, their habitats and/or to vegetable crops.

As previously mentioned, the invention can be largely and efficiently applied to vegetable crops of soybean, cotton, beans, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn, among others, to control and combat Euchistus herus, Nezara vihdula, Piezodorus guidini, Dichelops furcatus, Edessa meditabunda, Anticarsia gemmatalis, Pseudoplusia includens, Anthonomus grandis, Alabama argilacea, Spodoptera eridanea, Pectinophora gossipiela, Diabrotica speciosa, Empoaska kraemeri, Bemisia tabaci, Pseudaletia sequax, Dichelops furcatus, Rhopalosiphum graminum, Lyriomyza huidobrensis, Phthorimaea operculella, Lyriomyza trifolii and Thripes palmi, with no limitation, and the diseases generated by them.

In order to reach a better understanding of the invention, below we present some examples of formulations used with it. These examples intend to exemplify, not to limit the uses of the invention.

EXAMPLES:

Example 1 - Formulation of invention (BF 404-06):

(components) concen ration (g/100mL)]

Example 2 - Formulation of invention (BF 404-06): (components) [concentration (g/100mL)]

Water qsp

Silicon emulsion 0.5

EO/PO Copolymer 4

Sodium sulphonate naphthalene formaldehyde 2.5

Benzisotiazolin 0.25

Bentonite clay 0

Glycerin 8

Xanthan gum 0.4

Imidacloprid 10

Bifenthrin 3

Example 3 - Formulation of invention (BF 404-06):

(components) [concentration (g/1 OOrr

Water qsp

Silicon emulsion 0.5

EO/PO Copolymer 3

Isotridecyl alcohol with 8 mols of ethene oxide 1.5

Nonylphenol 10 mols of ethene oxide 1

Benzisotiazolin 0.25

Smectite clay 0.6

Monoethylene glycol 6

Xanthan gum 0.2

Imidacloprid 10

Bifenthrin 3 Example 4 - Formulation of invention (BF 404-06):

Example 5 - Use of BF 404-06 in soybean crops to combat bed bugs:

BF 404-06 in the dose of 0.5L/ha is applied to a soybean crop. With this dose, we use 5gia/ha of bifenthrin + 50gia/ha of imidacloprid. This dose is equivalent to 0.15L/ha of Talstar® (commercial name for bifenthrin 100, commercialized by FMC Quimica do Brasil Ltda.). Then, the same 15gia/ha of bifenthrin have been applied.

When comparing treatments, we can observe a pronounced gain in performance with the BF 404-06 treatment under the same proportion of active ingredient Talstar® for controlling bed bug Euchistus heros, a pest which bifenthrin doesn't have good efficacy with when applied alone.

These results, which are inserted in Tables 1 , 2 and 3 below, prove the results already obtained, and show the added and synergetic effect of imidacloprid and bifenthrin molecule, a fact that had never been observed in the state of the art for these doses in soybean crops.

The imidacloprid/bifenthrin ration might vary from 9:3 to 11 :3, and the ideal is 10:3, the exact proportion of tests.

TABLE 1 : Abstract of 3 studies accomplished in the Southern Region of Brazil, focusing the control of adult and nymph Euchistus herus bed bugs, 2008/09 crop.

TABLE 2: Abstract of 3 studies accomplished in the Southern Region of Brazil, focusing the control of adult and nymph Euchistus herus bed bugs, highlighting the residual insecticide control, 2008/09 crop.

Treatments Rate/ha % Control Euchistus herus NYMPHS

G AI Form 20AA 5 DAA 8 DAA 12 DAA 15 DAA

1 UNTREATED ( N insects/m) 4 5 5 5 5

1 2 BF 404-06 65(15>50) 0,5 70 ab 85 a 90 a l 1 69 ab 78 a 1

3 BF 404-06 78 (18+60) 0,6 87 a 85 a 94 a 80 a 85 a

4 BF 404-06 91 (21+70) 0,7 74 ab 87 a 100 a 79 a 80 a

1 TAI STAR G 0 15 45 b 55 b 41 be! 143 be 19 be 1

6 CONNECT 84 (9,3 +75) 0,75 65 ab 53 b 35 c 39 c 44 b

7 ENGEO PLENO 49,4 (19+25) 0,2 66 ab 63 b 70 ab 50 be 46 b

7 ENGEO PLENO 49,4 (19+25) 0,2 52 b 59 be 70 ab 29 b 36 b

TABLE 3: Abstract of 3 studies accomplished in the Central Region of Brazil (Cerrado), focusing the control of nymph Euchistus herus bed bugs, highlighting the residual insecticide control, 2008/09 crop.

Treatments Rate/ha % Control Euchistus he s ADULTOS & NINFAS

G Al Form 1 DAA 3 DAA 5 DAA 7 DAA 10 DAA IS DAA

1 UNTREATED ( N insects/m) 8 7 9 8 17 9

1 2 BF 404-06 65(Ϊ5 50) 0,5 88 a 91 a 79 a 72 a J 1 60 ab 78 ab 1

3 BF 404-06 78 (18+60) 0,6 91 a 90 a 93 a 79 a 67 ab 83 ab

4 BF 404-06 91 (21+70) 0,7 92 a 85 a 94 a 79 a 75 a 92 a

1 5 TALSTAR 0,15 73 b 55 b 44 b 45 b 1 1 52 b 69 b 1

6 CONNECT 84 (9,3 +75) 0,75 83 ab 72 ab 75 a 63 ab 56 b 69 b

7 ENGEO PLENO 49,4 (19+25) 0,2 88 a 84 a 83 a 72 a 61 ab 69 b

In order to obtain better identification and proof of the new, superior and unexpected technical effects of this invention, BF 404-06 was compared to standard commercial product Connect® (brand commercialized by Bayer Cropscience), which is composed by Betacyflutrin 12.5gia/L + imidacloprid 100gia/L. As the BF 404-06 has in its composition one of the active ingredients of Connect® - imidacloprid - this product was used as standard for results.

Aiming at controlling Euchistus heros, the dose of 70 to 100gia/ha of imidacloprid (Connect®) was used. For bifenthrin, when applied alone, it is used doses of 12 to 18gia/ha. With these doses, the control propitiated both by imidacloprid (Connect®) as well as by bifenthrin is generally insufficient and inconsistent.

Thus, in order to control this pest in the culture of soybean, when applying 0.5L/ha of formulated product BF 404-06 (bifenthrin + imidacloprid) against a dose of 0.75L/ha of standard commercial product Connect®, one can observe the following advantageous and surprising effects for technicians:

When applying BF 404-06, one uses 50% less active ingredient imidacloprid as compared to commercial product Connect®, i.e., with BF 404-06, one applies 50gia/ha, while with Connect®, one uses 75gia/ha to reach a satisfactory efficacy in the control of Euchistus herus in accordance with the data of Tables 4, 5 and 6 below.

The reduction in the quantity of this active ingredient propitiates advantages like: reduction of costs and less environmental impact due to the reduction of active ingredient/ha (decrease from 75gia/ha to 50gia/ha).

Besides the reduction of this active ingredient, we also observe a better control of the pest, mainly with insect nymphs (Table 5.). The extended residual effect brings the benefit of a lesser number of applications during the soybean crop cycle.

The control of bed bugs above exemplified can include a single, sequential or simultaneous application of BF 404-06.

The results can be observed in Table 5. The aim then was to exclusively control Euchistus herus nymphs. At 12 and 15 Days After the Application (DAA), the treatment with BF 404-06 shows efficiency of 70 and 62%, respectively, while with Talstar® applied alone it shows an efficiency of 32% in the same period. In order to show the consistency of results, the summary of studies accomplished in the region of Brazilian Cerrado (Table 6) also shows the same trend of the results previously mentioned.

Another important factor is the residual insecticide effect, which with BF 404-06 is extended. It is possible to observe that when analyzing data of Tables 4, 5 and 6, at 12 and 15 days after the application (DAA) of products. The treatment with BF 404-06 showed efficiencies of 70 and 62% respectively, while with Connect® the efficiency of the control was 35% and 41% in the same period.

In order to control this pest, several experiments were accomplished in different Brazilian regions. During these experiments, it has been applied 0.5L ha of formulated product BF 404-06 (bifenthrin + imidacloprid) and it was compared with Talstar® (bifenthrin) under the dose of 0.15L/ha, and with Connect® under the dose of 0.75LJha.

TABLE 4: Abstract of 5 studies accomplished in the Southern Region of Brazil, focusing the control of adult and nymph Euchistus herus bed bugs,

1 UNTREATED ( N insects/m)* 6 8 10 8 9

I 2 BF 404-06 65 (lSG-50]) 0,5 77 a 85 a 69 ab 70 a 62 ab 1

3 BF 404-06 78 (18460) 0,6 89 a 82 a 85 a 69 a 66 a

4 BF 404-06 91 (21+70) ^r 0,7 78 a 88 a 96 a 77 a 69 a

5 TALSTAR IS 0,15 50 b 53 b 39 c 32 b 32 c

I 6 CONNECT 84 (9.3C₊7S3> ^' 0.75 68 ab 49 b 34 c 35 b 41 bc l

7 EN6E0 PLENO 49,4 (19+25) 0,2 68 ab 59 b 43 be 38 b 39 be

TABLE 5: Abstract of 5 studies accomplished in the Southern Region of Brazil, focusing the control of nymph Euchistus herus bed bugs, highlighting the residual insecticide control, 2008/09 crop.

1 UNTREATED ( N insects/m 4 5 5 5 5 j 2 BF 404-06 65 {151 0,5 70 ab 85 a 90 | 69 ab 78 a l ^a f

3 BF 404-06 78 (18+60) 0,6 87 a 85 a 94 a 80 a 85 a

4 BF 404-06 91 (21+70) 0,7 74 ab 87 a 100 a 79 a 80 a

5 TALSTAR 15 0,15 45 b 55 b 41 be 43 be 19 be

J 6 CONNECT 84 (9,¾75j> 0,75 65 ab 53 b 35 c | | 39 c 44 «» 1

7 ENGEO PLENO 49,4 (19+25) 0,2 66 ab 63 70 ab 50 be 46 b

TABLE 6: Abstract of 3 studies accomplished in the Central Region of Brazil (Cerrado), focusing the control of nymph Euchistus herus bed bugs, highlighting the residual insecticide control, 2008/09 crop. treatments Rate/ha % Control Euchistus herus AOULTOS & NINFAS

?G AI¾ Form 1 DAA 3 DAA 1 5 DAA 7 DAA ID DAA 15 DAA

1 UNTREATED ( insects/m) 8 7 9 8 17 9

1 2 BF 404-06 65 (15(50-5 °f⁵ 88 a 91 a 79 a 72 a I I 60 ab 78 ab

,6 1

3 BF 404-06 78 (18+60) 0 91 a 90 a 93 a 79 a 67 ab 83 ab

4 BF 404-06 91 (21+70) 0,7 92 a 85 a 94 a 79 a 75 a 92 a

5 TALSTAR 15 0,15 73 b 55 b 44 b 45 b 52 b 69 b

1 6 CONNECT 84 (9,3 {75} 0,75 83 ab 72 ab 75 a 63 ab| f 56 b 69 b 1

7 ENGEO PL£NO 49,4 (19+25) 0,2 88 a 84 a 83 a 72 a 61 ab 69 b

Example 5 - Efficacy of BF 404-06 focusing the control of adult and nymph Euchistus herus bed bugs, Londrina/PR, 2007/08 crop.

This work was accomplished in order to check the efficacy of products to control the Euschistus heros bed bug, which is popularly known as brown soybean bed bug. Product BF 404-06 under the dose of 0.5L/ha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 90.1 % at 14 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0.15L/ha, control close to 70%. Connect®, which under these doses contains 75gia/l_ of imidacloprid, offers a dissatisfactory result, with 36% of control.

These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 150% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 28% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

TABLE 7

1 UNTREATED 2,5 a 0,0 b 0,0 c 0,0 e

2 BF 404-06 39 0,3 3,0 a 87,5 a · 96,9 a 83,2 ab

|3 BP 464-66 65 6,5 1 ,8 a 95,0 a 100,0 a SiU a 1

4 BF 404-06 91 0,7 3,0 a 95,8 a 100,0 a 93,8 a

5 TALSTAR 15 0,15 2,0 a 57,5 a 64,1 ab 70,3 bcj

6 CONNECT 84 0,75 1 ,3 a 16,7 b 76,6 a 36,7 d I

7 ENGEO PLENO 44,4 0,18 2,0 a 24,2 b 44,0 b 61 ,3 c d.m.s (P=.05) 2,12 33,20 25,38 15,57

Desvio Padrao 1 ,43 22,35 17,08 10,48

CV 64,44 41,53 24,83 16,85

Example 6 - Efficacy of BF 404-06 focusing the control of adult and nymph Euchistus herus bed bugs, Passo Fundo/RS, 2007/08 crop.

This work was accomplished in a region that is considered to be colder in order to check the efficacy of products to control the Euschistus heros bed bug, which is popularly known as brown soybean bed bug.

Product BF 404-06 under the dose of 0.5L/ha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 66% at 15 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0.15L/ha, control close to 60%. Connect®, which under these doses contains 75gia/L of imidacloprid, offers a dissatisfactory result, with 44% of control. These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 53% better than Connect®, which contains 75gia/ha of imidacloprid, and is 9% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

TABLE 8

D< - 1 « ,i % Contr ote Euchlstas, hen/s

frratainentOT - ^{" "l} GIA 5 DAA 3 DAA ^ 15ΏΑΑ·

1 UNTREATED 0,0 b 0,0 b 0,0 c 0,0 b 0,0 b

2 BF 404-06 39 0,3 43,6 a 45,3 a 47,7 ab 34,9 a 44,7 ab

I 3 BF 404-06 65 0,5 58,1 a 60,2 a 60,0 a 59,7 a 66,1 a I

4 BF 404-06 91 0,7 59,5 a 54,7 a 62,6 a 68,0 a 60,0 ab

5 TALSTAR 15 0,15 56,3 a 37,5 a 38,0 abc 56,1 a 60,7 a

6 CONNECT 84 0,75 64,4 a 56,9 a 36,1 abc 45,8 a 43,8 ab d.m.s (P=.05) 27,36 32,06 28,72 28,98 39,15

Desvio Padrao 18,41 21 ,58 19,33 19,51 26,35

CV 36,82 48,29 56,96 39,93 54,98

Example 7 - Efficacy of BF 404-06 focusing the control of adult and nymph Pseudoplusia includens caterpillars, Londrina/PR, 2007/08 crop.

This work was accomplished aiming at controlling the Pseudoplusia includens caterpillar, which is currently one of the most difficult pests to control in soybean crops, in order to check the efficacy of products to control the mentioned pest, which is popularly known as Soybean Looper.

Product BF 404-06 under the dose of 0.5L/ha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 85% at 9 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0.15L/ha, control close to 65%. Connect®, which under these doses contains 75gia/L of imidacloprid, shows a result slightly inferior to BF 404-06 under the same proportion of active ingredient imidacloprid per ha. These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 4% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 30% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

TABLE 9

Doses ¾ - %¾ontrole Pseudoplusia includens %

Tratamentos GIA Formulado ¾. - 5 DAA 9:DAA

1 UNTREATED 0,0 b 0,0 c

2 BF 404-06 39 0,3 30,0 ab 65,8 ab

|3 BF 404-66 65 6.S 65,0 ab 85 ab

4 BF 404-06 91 0J 100,0 a 97,2 a

5 TALSTAR 15 0,15 33,3 ab 65,0 ab

6 CONNECT 84 0,75 36,7 ab 81 ,7 ab d.m.s (P=.05) 57,50 ^' 26,79

Desvio Padrao 38,70 18,03

CV 93,42 28,67

Example 8 - Abstract of efficacy of 3 studies with BF 404-06 focusing the control of adult and nymph of the small green stink bug (Piezodorus guidinii), Mato Grosso/MT, 2007/08 crop.

The Piezodorus guidinii bed bug, popularly known as small green stink bug, is also a species that causes big production losses in soybean cultures, which can reach nearly 40% according to studies accomplished by Dr. Cecilia Czapak from the Federal University of Goias, published in Cultivar magazine in January, 2009.

The work below shows synthetized results of 3 experimental studies accomplished in the central-western region of Brazil, regarding the control of this pest. Product BF 404-06 under the dose of 0.5Uha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 49% at 15 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0.15L/ha, control close to 32%. Connect®, which under these doses contains 75gia/L of imidacloprid, offers an overall result of 40% of control. These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 22.5% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 53% better than Talstar® under the same quantity of active ingredient bifenthrin/ha. TABLE 10

|Contfole(%j^otf^s^(f-fimJ

It-.oimulado] ■3DAA¾ ■7DAA1 K!ODAAl R5PAA1

1 UNTREATED O c O d O d O b O b 0,0 b

2 BF 404-06 9 + 30 0,3 80 b 68 b 68 abc 69 a 65 a 46 a

I 3 BF 404-06 15 + 50 0.5 91 ab 78 ab 78 ab 79 a 57 a 49 a I

4 BF 404-06 21 + 70 0.7 85 ab 74 ab 74 abc 77 a 56 a 38ab

5 TALSTAR 15 0,15 91 ab 51 c 51 c 67 a 55 a 32 ab

6 CONNECT 9,3 + 75 0,75 92 ab 56 be 56 be 66 a 45 a 40 ab

Example 9 - Abstract of efficacy of 14 studies with BF 404-06 focusing the control of adult and nymph of the neotropical brown stink bug (Euchistus heros), Brazil/MT, 2007/08 crop.

The work below shows the synthetized results of 14 experimental studies accomplished in the central-western region of Brazil, which has a hot climate that favors a rapid multiplication of insects considered pests for the agriculture. These works were accomplished with the objective of checking the efficacy of products to control nymphs of the Euschistus heros bed bug, popularly known as brown stink bug, thus assessing the reinfestation of the pest.

Product BF 404-06 under the dose of 0.5Uha ( 5 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 85% at 20 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0. 5L/ha, control close to 73%. Connect®, which under these doses contains 75gia/l_ of imidacloprid, offers a dissatisfactory result of 68% of control.

These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 25% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 16% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

Thus, we can have less applications by using the treatment with BF 404-06 under the 0.5L/ha dose (15 + 50gia/ha de bifentrina + imidacloprid), because its control of nymphs was better.

TABLE 1 1 Tratamerrtos Doses (ha) Controls %) Euschistus hems Ninfas

GIA Formulado 3DAA 5DAA 7DAA 10DAA 15DAA 20DAA

1 UNTREATED 0 b 0 c 0 c 0 c 0 b 0 b

2 BF 404-06 9 + 30 0,3 84 a 98 ab 82 ab 79 ab 84 a 83 a

13 BF 404-06 15 + 50 0,5 80 a 83 b 80 ab 90 a 76 a 85 a I

4 BF 404-06 21 + 70 0,7 84 a 89 ab 94 a 94 a 89 a 95 a

5 TALSTAR 15 0,15 76 a 91 ab 74 b 66 b 70 a 73 a

6 CONNECT 9,3 + 75 0,75 72 a 89 ab 79 ab 80 ab 87 a 68 a

7 ENGEO PLENO 19 + 25 0,18 44 ab 100 a 77 ab 81 ab 69 a 74 a

Example 0 - Efficacy of BF 404-06 focusing the control of adult Euchistus herus bed bugs, Ibipora/PR, 2008/09 crop.

This work was accomplished in order to check the efficacy of products to control the Euschistus heros bed bug, which is popularly known as brown soybean bed bug.

Product BF 404-06 under the dose of 0.5LJha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of nearly 70% at 14 days after application (DAA), while Talstar® (bifenthrin 10Ogia/L) offers, under the dose of 0.15l_ ha, control close to 43%. Connect®, which under these doses contains 75gia/L of imidacloprid, offers a dissatisfactory result of 28% of control.

These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 150% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 62% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

This crop developed under high rainfall. As bifenthrin has low solubility, the product remains longer on top of soybean leaves, which propitiates more time for the control, and results in big differences regarding standard products Connect® and Engeo Pleno® (brand distributed by Syngenta).

TABLE 12

Treatments Rate/ha V....": insetos % Control El ch istus herus ADULTS

6 A) Formulated ODAA 2 DAA 5 DAA 7 DAA 10 DAA 14 DAA

1 UNTREATED ( N nsects/m) 5 a 3 a 7 a 5 a 4 a 4 a

1 2 BF 404-06 65 (15+50) 0,5 4 a 72.9 a 85.6 a 60,4 ab 77,7 a 69,2 a 1

3 BF 404-06 78 (18+60) 0,6 4 a 91,7 a 71,1 a 59,7 ab 63,1 a 60,8 a

4 BF 404-06 91 (21+70) 0,7 4 a 87,5 a 77,8 a 91,7 a 76,2 a 72,5 a

5 TALSTAR 15 0,15 4 a 18,8 b 88,7 a 22,9 be 30,4 ab 43,3 ab

6 CONNECT 84 (9,3 +75) 0,75 2 a 75,0 a 82,4 a 27,8 be 34,2 ab 28,3 ab

7 ENGEO PLENO 49,4 (19+25) 0,2 4 a 18,8 b 44,2 b 22 be 28,9 ab 31,7 ab

LSD (P=.05) 35,22 19,28 27,18 34,82 36,08

Standard Deviation 23,71 12,98 18,30 23,44 24,28

CV 45,52 20,19 44,87 52,86 55,58 Example 11 : Efficacy of BF 404-06 focusing the control of nymphs of the Euchistus herus bed bug, Ibipora/PR. 2008/09 crop:

The work below proves the excellent results of BF 404-06. This work was accomplished with the objective of checking the efficacy of products involved in the control of nymphs of the Euschistus he s bed bug, popularly known as brown stink bug, thus assessing the reinfestation of the pest.

In this study, the reinfestation was evidenced at 14 DAA, because at 10 DAA there was only 1 bed bug per square meter in average in the plot without chemical treatment, while at 14 DAA the infestation increased, reaching the average of 4 bed bugs per square meter.

Product BF 404-06 under the dose of 0.5Uha (15 + 50gia/ha of bifenthrin + imidacloprid, respectively) offers control of 100% at 14 days after application (DAA), while Talstar® (bifenthrin 100gia/L) offers, under the dose of 0.15Uha, control close to 10%. Connect®, which under these doses contains 75gia/L of imidacloprid, offers a dissatisfactory result of 42,5% of control.

These results show that BF 404-06, even with 50% less imidacloprid, propitiated final control 135% better than Connect®, which contains 75gia/ha of imidacloprid in its formulation, and is 900% better than Talstar® under the same quantity of active ingredient bifenthrin/ha.

Thus, we can have less applications by using the treatment with BF 404-06 under the 0.5L/ha dose (15 + 50gia/ha de bifentrina + imidacloprida), because its control of nymphs was better.

TABLE 13

Treatments Rate/t ¾ Control ε jchisnis hen s YMPHS .

. : G AI. F ormulatec 0 DAA 7 DAA 10 DAA 14 DAA

1 UNTREATED ( N insects/m) 2 a 3 a 6 a 3 a 1 a 4 a

1 7 RF 404-06 65 (15+50) 0.5 2 a , 88 a 85.8 ab 91.7 a 50.0 a 100.0 a 1

3 BF 404-06 78 (18+60) 0,6 3 a 100 a 95,8 a 91,7 a 50,0 a 100,0 a

4 BF 404-06 91 (21+70) o,7.„ 5 a 100 a 87,5 ab 100,0 a 50,0 a 100,0 a

5 TALSTAR 15 0,15 2 a 46 b 89,4 ab 72,9 a 25,0 a 10,0 be

6 CONNECT 84 (9.3 +75) 0.75 4 a 63 ab 45.6 b 58.3 a 50,0 a 42.5 b

7 ENGEO PLENO 49,4 (19+25) 0,2 4 a 71 ab 64,4 ab 85,4 a 25,0 a 22,5 be

LSD (P=.05) 3,7 30,6 31,60 3152 44,88 31,08

Standard Deviation ^•2,5 20,6 21,27 2121 30,21 20,92

CV 79,2 30,94 31,78 29,7 84,59 39,05

Claims

1. An agrochemically synergistic formulation, characterized by comprising:

(i) imidacloprid;

(ii) bifenthrin; and

(iii) suitable adjuvants, carriers and/or excipients; wherein the ratio of imidacloprid:bifenthrin in the formulation is about 8-12:1- 5, preferably about 10:3.

2. The formulation according to claim 1 , characterized in that it comprises about 1 to about 699gia/L of bifenthrin and about 699 to about

1gia/L of imidacloprid, preferably about 30gia/L of bifenthrin and about 100gia/L of imidacloprid.

3. The formulation according to claim 1 , characterized in that it comprises a total of about 10 to about 700gia/L of bifenthrin and imidacloprid, preferably about 130gia/L.

4. The formulation according to any one of claims 1 to 3, characterized in that the suitable adjuvants, carriers and/or excipients are selected from the group consisting of: water, surfactants, antifoaming agents, rheology modifiers, dispersing agents, wetting agents, bacteriostatic or bactericide agents, colorants/dyestuff, antiagglomerating agents, stabilizers, antifreezing agents, clay, silicates, silica, resins, waxes, cellulosic fibers, fertilizers, C1-C14 alcohols, glycols, acetates, ketones, glycerides, saturated or unsaturated hydrocarbons, fatty acid esters, vegetable oils, mineral oils, and mixtures thereof.

5. The formulation according to any one of claims 1 to 4, characterized in that it is in the solid or liquid form, preferably the solid form is a wet powder (PM) and/or water-dispersed granules (WDG) and the liquid form is an emulsified concentrate (EC), concentrated suspension (SC), suspoemulsion (SE) and/or concentrated emulsion (EW).

6. The formulation according to any one of claims 1 to 5, characterized in that it comprises: com onents concentration / OOmL)]

7. The formulation according to any one of claims 1 to 5, characterized in that it comprises:

com onents concentration /1 OOmL)]

8. The formulation according to any one of claims 1 to 5, characterized in that it comprises: com onents concentration /100mL)]

9. The formulation according to any one of claims 1 to 5, characterized in that it comprises:

com onents [concentration (g/100mL)]

10. A process for preparing an agrochemically synergic formulation, as defined in any one of claims 1 to 9, characterized by comprising the steps of :

after the recrystallization process is concluded, Imidacloprid is added;

after all raw materials have been added, the formulation undergoes a grinding process, in which there will be more interaction among molecules and reduction of active ingredients particle size, thus increasing the synergism between molecules and their efficacy in the field;

after being grinded, the formulation undergoes a process of deaeration and densification to increase its physical stability, then obtaining a stable and synergetic agrochemical formulation;

then, it is bottled in high density polyethylene bottles/jerricans and distributed in the market.

11. An use of imidacloprid and bifenthrin, characterized by being in the manufacture of an agrochemically synergistic formulation for controlling and/or combating plagues and diseases caused therefrom in vegetable cultures.

12. An use of the agrochemically synergistic formulation as defined in any one of claims 1 to 9, characterized by being for controlling and/or combating plagues and diseases caused therefrom in vegetable cultures.

13. The use according to any one of claims 11 and 12, characterized in that the cultures are selected from soybean, cotton, bean, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn, among others and the plagues are selected from Euchistus herus, Nezara viridula, Piezodorus guidini, Dichelops furcatus, Edessa meditabunda, Anticarsia gemmatalis, Pseudoplusia includens, Anthonomus grandis, Alabama argilacea, Spodoptera endanea, Pectinophora gossipiela, Diabrotica speciosa, Empoaska kraemeri, Bemisia tabaci, Pseudaletia sequax, Dichelops furcatus, Rhopalosiphum graminum, Lyriomyza huidobrensis, Phthohmaea operculella, Lyriomyza trifolii, and Thripes palmi.

14. The use according to any one of claims 11 to 13, characterized in that the formulation is employed in a single, sequential or simultaneous application.

15. A method for controlling and/or combating plagues and diseases in vegetable cultures, characterized by comprising applying the agrochemica!ly synergistic formulation as defined in any one of claims 1 to 9, over said plagues, their habitat and/or vegetable cultures.

16. The method according to claim 15, characterized in that the cultures are selected from soybean, cotton, bean, wheat, irrigated rice, potato, tomato, citrus, tobacco and corn, among others and the plagues are selected from Euchistus hews, Nezara viridula, Piezodorus guidini, Dichelops furcatus, Edessa meditabunda, Anticarsia gemmatalis, Pseudoplusia includens, Anthonomus grandis, Alabama argilacea, Spodoptera eridanea, Pectinophora gossipiela, Diabrotica speciosa, Empoaska kraeme , Bemisia tabaci, Pseudaletia sequax, Dichelops furcatus, Rhopalosiphum graminum, Lyriomyza huidobrensis, Phthohmaea operculella, Lyriomyza trifolii, and Thripes palmi.

17. The method according to any one of claims 15 and 16, characterized in that the formulation is employed in a single, sequential or simultaneous application.