Agrochemical Composition
The present invention relates to a new agrochemical composition, its method of manufacturing , and a method for using the composition. In the field of fertilizers, it is known to fabricate water-soluble sticks that can be inserted into the ground around trees and plants. However it is not known to insert such a stick into a tree without substantially damaging the tree.
In the field of phytoprotection products, there exists a need to provide more efficient means of delivery of the products to the plants requiring protection. The need for greater efficiency stems from a concern to not place the products where they are not needed and to decrease the required dose level of the products where they are required for protection of plants.
Placement of phytoprotection products on or in the ground around trees does not obviate this problem. There also exists a need to provide the delivery means of the said products in a manner which cannot easily contaminate the users of the product.
It is an object of the present invention to provide a new delivery means for phytoprotection products.
Another object of the present invention is to provide a new means of delivery of phytoprotection products which can lower the required dose per plant.
Another object of the present invention is to provide a new means of delivery of phytoprotection products which are generally less available for contamination of a user of the product.
Another object of the present invention is to provide a new means of delivery of phytoprotection products which are generally less available for contamination of the environment.
These objects are met in whole or in part by the instant invention. The present invention relates to a shaped article for insertion into a plant or tree which article comprises a plant-mobile phytoprotection product and a water- soluble carrier.
By plant-mobile is meant the property of being able to be translocated from one part of the plant to another part, for example from a root to a leaf or from a trunk to a leaf. More preferably, the phytoprotection product is substantially water- soluble. The water solubility of the phytoprotection product at substantially neutral pH is generally from 0.5 to 500 grams per liter of water, preferably from 3 to 350 grams per liter of water, more preferably from 100 to 300 grams per liter of water. The article of the invention is substantially rapidly dispersed in the tree. By the term "rapidly" is meant that from 50% to 100% of the article is generally dissolved or suspended in the substance of the tree after from five minutes to two days, preferably after from ten minutes to one day, most preferably after from thirty minutes to twelve hours.
The phytoprotection product generally is an insecticide, nematicide, fungicide, or plant growth regulator.
Fungicides that may be used according to the instant invention include: a phosphorous acid derivative, preferably an alkyl phosphorous acid derivative, most preferably the aluminium salt of ethyl hydrogen phosphonate (fosetyl -Al); methyl l-(butylcarbamoyl)benzimidazol-2-ylcarbamate (benomyl); triazoles including (±)-l-[2-(2,4-dichlorophenyl)-4-propyl-l,3-dioxolan-2- ylmethy 1]- 1 H- 1 ,2,4-triazole (propiconazole); and l-[(2RS,4RS:2RS,4SR)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]- lH-l,2,4-triazole (bromuconazole);
Plant growth regulators that may be used according to the instant invention include: a gibberellin such as gibberellic acid; a cytokinin;and
2-chloroethylphosphonic acid (ethephon).
Insecticides or nematicides that can be used according to the instant invention either alone or in combination with other pesticides include:
nitromethylenes or nitronimines including l-(6-chloro-3-pyridylmethyl)-N- nitroimidazolidin-2-ylideneamine (imidacloprid) cyanoimines including (E)-N1-[(6-chloro-3-pyridyl)methyl-N2-cyano-N1- methylacetamidine (acetamiprid); and organophosphates including S,S-di-sec-butyl O-ethyl phosphorodithioate
(cadusofos);
O-ethyl S,S-dipropyl phosphorodithioate (ethoprophos); and
(RS)-S-5ec-butyl O-ethyl-2-oxo-l,3-thiazolidin-3-ylphosphonothioate (fosthiazate); and carbamates including 2-methyl-2-(methylthio)propionaldehyde-O- methy lcarbamoy loxime(aldicarb) .
Other insecticides or nematicides that can be used according to the instant invention either alone or in combination with other pesticides include compounds of formula (I):
(I) wherein:
R\ is CN or methyl;
R2 is S(O)nR3;
R3 is alkyl or haloalkyl; R4 is selected from the group consisting of hydrogen, halogen, -NR5R6, -
C(O)OR7, -S(O)mR7, alkyl, haloalkyl, -OR8, -N=C(R9)(R10) and
C(O)alkyl;
R5 and R are independently selected from a hydrogen atom, alkyl, haloalkyl,
-C(O)alkyl, -C(O)OR75 -S(O)rCF3; or R5 and Rg form together a divalent alkylene radical which may be interrupted by one or more heteroatoms, preferably selected from oxygen, nitrogen and sulfur; R7 is selected from alkyl and haloalkyl;
Rg is selected from alkyl, haloalkyl and hydrogen;
R9 is selected from hydrogen and alkyl;
RlO is selected from phenyl or heteroaryl each of which is unsubstituted or substituted by one or more hydroxy, halogen, -O-alkyl, -S-alkyl, cyano, or alkyl or combinations thereof;
X is selected from nitrogen and -C-R12;
R\ \ and R12 are independently selected from halogen or hydrogen; Rl3 is selected from halogen, haloalkyl, haloalkoxy, -S(O)qCF3, -SF5; m, n, q, r are independently selected from 0, 1, and 2; provided that when R\ is methyl, R3 is haloalkyl, R4 is NH2, Ri 1 is Cl, R13 is CF3, and X is N.
The alkyl and alkoxy groups and moieties thereof of the formula (I) are preferably lower alkyl and alkoxy groups, that is, groups having one to six carbon atoms. The haloalkyl and haloalkoxy groups likewise preferably have one to four carbon atoms. The haloalkyl and haloalkoxy groups can bear one or more halogen atoms; preferred groups of this type include -CF3 and -OCF3. It shall be understood that the ring formed by the divalent alkylene radical represented by R5 and Rg and including the nitrogen atom to which R5 and Rg are attached is generally a 5, 6, or 7-membered ring. When R10 is heteroaryl, it is preferably pyridyl, most preferably 2-pyridyl. It will be understood that the 1-arylpyrazoles of formula (I) include enantiomers and/or diastereomers thereof.
A preferred group of 1 -arylpyrazoles for use in the present invention are those of formula (I) with one or more of the following features wherein: R\ is CN;
R4 is -NR5R6; R5 and Rg are independently selected from the hydrogen atom, alkyl, haloalkyl, C(O)alkyl, C(O)OR7; X is C-R12; or
R\ is selected from a halogen atom, haloalkyl, haloalkoxy, and -SF5. Another preferred group of 1 -arylpyrazoles of formula (I) for use in the present invention is that wherein: Rl is CN;
R3 is a haloalkyl radical; R4 is NH2; X is C-Rι2;
R\ 1 and R^2 represent, independently of one another, a halogen atom; and Rl3 is a haloalkyl radical.
Specifically preferred compounds of formula (I) are 5-amino-l -(2,6-dichloro 4-trifiuoromethyl phenyl) 4-trifluoromethylsulfιnyl-3-cyanopyrazole or 5-amino-l - (2,6-dichloro 4-trifluoromethyl phenyl)-4-ethylsulfιnyl-3-cyanopyrazole.
Compounds of formula (I) may be prepared according to known processes, for example as described in International Patent Publications No. WO 87/03781, WO 93/06089 and WO 94/21606, as well as in European Patent Publication numbers 295117, 403300, 385809 or 679650, German Patent Publication 19511269 and United States Patents 5,232,940 and 5,236,938 or other process according to the knowledge of a man skilled in the art of chemical synthesis. Other phytoprotection products specifically
named supra may be prepared according to The Pesticide Manual, tenth edition, British Crop Protection Council.
By the term "water soluble carrier" is meant an organic or inorganic material which can be natural or synthetic, monomeric or polymeric, which is associated with the active ingredient and which facilitates its application to the locus to be treated. The carrier is generally inert and should be agriculturally acceptable, especially on the contemplated or treated locus or crop. Preferably the water-soluble carrier is selected from:
Dicalcium phosphate; microcrystalline cellulose; polyvinylpyrrolidinone; methyl vinyl ether- maleic anhydride copolymer; polyacrylic acid polymer;and maltodextrin. Another group of preferred water soluble carriers are sugars which includes materials having a chemical formula of CnH2nOn or CnH2n.2On.,. By the term sugars is also meant derivatives of sugars which can be effected by chemical reaction or transformation. Sugars are also generally known as monosaccharides and polysaccarides and derivatives thereof. Particularly preferred sugars are sucrose, glucose, dextrose, lactose and fructose.
The article may also contain a disintegrant which is generally known to the skilled addressee. Examples of disintegrants include starches; modified starches; microcrystalline cellulose; water soluble cellulose derivatives, for example methyl cellulose, sodium carboxymethylcellulose, hydroxypropyl methyl cellulose; alginates such as alginic acid or sodium alginate; and clays such as veegum. In order to facilitate the preparation of the article, the article may also comprise a lubricant. Examples of lubricants include metallic stearates, for example magnesium, calcium or zinc stearate, stearic acid; and vegetable oil. Preferably, the article comprises an agrochemically acceptable adjuvant which is generally known to the skilled adressee. Adjuvants include surfactants as well as other ingredients
such as dispersants, stickers, antifreezing agents, dyestuffs, adhesives, protective colloids, penetrating agents, stabilizing agents, sequestering agents, antiflocculating agents, corrosion inhibitors, pigments and polymers. Adjuvants are generally known to the skilled artisan in the field of phytoprotection products. The surfactants can be of the emulsifying or wetting type, ionic or non-ionic and include salts of polyacrylic or lignosulfonic acids; salts of phenolsulfonic or naphthalenesulfonic acids; polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines or substituted phenols (particularly alkylphenols or arylphenols); ester-salts of sulfosuccinic acids; taurine derivatives, such as alkyl taurates; phosphoric esters; or esters of alcohols or polyoxyethylated phenols. Such additives include: Trade Name Chemical Description
Ethylan BCP Nonylphenol ethylene oxide condensate
Soprophor BSU Tristyrylphenol ethylene oxide condensate
Arylan CA A 70% w/v solution of calcium dodecylbenzenesulfonate
Solvesso 150 Light Cio aromatic solvent
Arylan S Sodium dodecylbenzenesulfonate
Darvan No2 Sodium lignosulphonate
Celite PF Synthetic magnesium silicate carrier
Sopropon T36 Sodium salts of polycarboxylic acids
Rhodigel 23 Polysaccharide xanthan gum
Bentone 38 Organic derivative of magnesium montmorillonite
Aerosil Microfine silicon dioxide
The percentage of active ingredient in the article can vary widely and depends on the maintenance of the rigidity of the article. Generally the percentage of active ingredient in the article varies from 1 percent (%) to 80 percent (%) by weight, preferably from 5% to 75% and most preferably from 30%) to 50%.
The percentage of carrier varies in order to maintain the rigidity of the article. Generally the percentage of carrier in the article varies from 1 percent (%) to
80 percent (%>) by weight, preferably from 5% to 75%> and most preferably from 30% to 50%.
The percentage of adjuvant varies in order to maintain the rigidity of the article. Generally the percentage of adjuvant in the article varies from 1 percent (%) to 80 percent (%) by weight, preferably from 5%> to 75%).
The percentage of disintegrant is generally from 0.5 to 5% of the weight of the article, preferably from 1 to 4%, preferably from 2 to3%>.
The percentage of lubricant is generally from 0.1 to 1% of the weight of the article, preferably from 0.3 to 0.7 %>. The weight/weight ratio of active ingredient to water soluble carrier generally varies from 1:99 to 99:1, preferably from 5:95 to 95:5 mostpreferably from 20:80 to 80:20.
When the active ingredient is a fungicide, preferably fosetyl-Al, the weight percent of the sum of active ingredient and the carrier is generally from 80 to95%, preferably from 80%> to 90% of the total weight of the article. When the active ingredient is an insecticide, preferably aldicarb, the weight percent of the sum of active ingredient and the carrier is generally from 10 to 35%>, preferably from 12% to 25%) of the total weight of the article
The article is preferably substantially dustless. By the term "dustless" is meant that when the article is contacted by human skin or brushed by clothing or gripped or rubbed by the hand that matter is not lost from the article. Another preferred feature of the invention is an article that comprises a coating on the outside of the article, preferably a plastics coating. The coating substantially reduces the risk of exposure to the phytoprotection product and prevents invasion of water or humidity into the article, thus fouling it. The coating also creates another barrier to prevent the loss of matter from the article and human contact with the phytoprotection product of the article.
The size of the article is generally such that it may be grasped substantially entirely within a human hand. However, the invention also comprises a series of articles according to the invention which are linked end-to-end. Such an
embodiment of the invention is generally the result of a manufacturing process in which the articles are mechanically extruded and divided into sections capable of being grasped by the human hand.
The length of the article is generally greater than 4 times the largest cross- section of the article, preferably greater than 8 times the cross section. The length is generally from two to ten centimeters. However, the dimensions of the article will vary according to the dose necessary for the plant and the percentage of phytoprotection product required per article.
In a preferred embodiment, the article is a rod or in the shape of a rod. The cross-section of the article at any point is generally polygonal, preferably substantially square or rectangular. The article at one end partially tapers toward a point, the taper forming a conical or partially conical section. This tapering generally allows the article to be pushed into a plant or tree via a longitudinal force applied at the other end. Preferably the article tapers to a point. The article generally is able to resist breakage and compression from a longitudinal force necessary to push the rod into a tree or plant which the bark or core of the said tree or plant is not able to resist. Preferably the tree or plant is a banana tree, plantain tree or a pineapple plant.
The longitudinal force is preferentially applied at the non-tapering end of the article by hand or alternatively by a pushing means. The pushing means generally comprises a hammer or rod insertion device.
By the term "rigid" is meant generally unbendable or deformable along the length of the article. That is, when a force is applied across the length, rather than bend or substantially warp in shape, the article will fissure or break into individual pieces. Preferably the article is not breakable by substantial effort of the human hand.
The invention also comprises a commercial product containing an article or a series of articles linked end to end which can be disconnected for individual use. The preparation of the article can be effected by a process known to those skilled in the art. Generally the phytoprotection product is admixed with a suitable
carrier and optionally an adjuvant to produce a granular formulation and compressed in a mold under sufficient pressure to form the article. A sufficient pressure preferably includes pressures from about 300 megadynes (Mdyne) per cm2 to about 900 Mdyne/cm2.The invention also relates to a method of treatment of a plant or a tree, preferably a banana or plantain or pineapple plant by the use of an article comprising a plant-mobile phytoprotection product and a water soluble carrier. The article is implanted in the tree or plant at an appropriate stage to protect the plant from the desired pest. In the case of fosetyl-Al, the article is implanted in a banana tree just before the flowering stage of the tree. The article may also be placed in a cut surface of a banana tree.
An additional aspect of the invention is a banana improved by the method of treatment, as well as a commercial product comprising the article of the invention. The banana is a commercial consequence of the method of treatment.
Another aspect of the invention is a method of reducing worker exposure to a phytoprotection product used at a locus, which locus comprises banana, plantain or pineapple trees or plants which method comprises the use of an article as defined above. The article of the invention preferably provides a reduction in the ratio of the amount of the dose of phytoprotection product to surface area of the dosage form. In the prior art, the dose of product is generally administered as a granular or liquid composition, which provides a substantial possibility of worker exposure by inhalation or dermal absorption of the product. With the article of the invention, the said ratio is reduced by orders of magnitude, from 102 to 108, preferably from 103 to 106.
The following non-limiting examples exemplify the present invention.
Example 1 :
About 3.75 g of 80:0.5:19.5 fosetyl-Al (as Aliette® 80%> water dispersible granules) : magnesium stearate : lactose were placed in a steel die and compressed in a Coulton 341 tabulating press at about 690Mdynes/cm2 to provide a rod with a tapered end about 4 cm long by 0.75 cm diameter.
Example 2:
The procedure of Example 1 is repeated using 3.75 g mixture of 40:0.5:59.5 of fosetyl-Al (as Aliette® 80%> water dispersible granules) : magnesium stearate : lactose.
Example 3:
The procedure of Example 1 is repeated using 3.75 g mixture of 40:0.5:59.5 of fosetyl-Al (as Aliette® 80%) water dispersible granules) : magnesium stearate : dicalcium phosphate.
Example 4:
The procedure of Example 1 is repeated using 3.75 g mixture of 40:0.5:59.5 of fosetyl-Al (as Aliette® 80% water dispersible granules) : magnesium stearate : microcrystalline cellulose.
Example 5:
A 10 gram mixture of the aluminium salt of ethyl hydrogen phosphonate , Carbowax™ 8000, Tixosil 38AB and dextrose in a ratio of 30.8:4:2:63.2 was compressed in a steel dye at about 690Mdynes/cm2 into a round tablet approximately 23 mm in diameter and 4 mm thick.
Example 6
A mixture of Aliette Signature MC®, lactose, microcrystalline cellulose, sodium carboxymethyl cellulose and magnesium stearate in a ratio of
68.18:24.32:5:2:0.5 are compressed as in Example 1 to provide a six gram tablet tapered for insertion.
Example 7
A mixture of aldicarb as Temik® 15G granules, lactose, sodium carboxymethyl cellulose and magnesium stearate in a ratio of 77.5:20:2:0.5 are compressed as in Example 1 to provide a fifteen gram tablet tapered for insertion.
Example 8:
An article as described in any one of Examples 1 -7 pushed by hand into the pseudostem of a banana tree. After twenty-four hours, the rod is substantially dissolved. No active ingredient is outside the treated banana tree. There is substantially no worker exposure to the active ingredient.