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    • 专利摘要:
    The present invention relates to the composition of a concentrated suspension comprising (expressed by weight relative to the total weight of the composition): a) 40 to 80%, preferably 40 to 70%, of dodecylguanidine particles, a salt or a ester thereof, b) 0 to 10% of an anti-freeze compound, c) 1 to 10% of a wetting agent and / or, d) a dispersing agent, e) 0 to 5% of an antifoaming agent, f) the remainder of water, characterized in that the median particle diameter (d 50) is at least 7um and less than 40um.
    公开号:BE1020016A3
    申请号:E2012/0558
    申请日:2012-08-22
    公开日:2013-03-05
    发明作者:Alan Pirotte
    申请人:Agriphar S A；
    IPC主号:
    专利说明:

    IMPROVED AQUEOUS CONCENTRATED SUSPENSION, USE AND PROCESS FOR PRODUCTION THEREOF
    TECHNICAL AREA
    The present invention relates to the technical field of active substance formulations in the context of their use for the protection of crops. More specifically, the invention relates to an aqueous concentrated suspension comprising dodecylguanidine or a salt, an ester or a derivative. The invention also relates to a process for the production thereof and the use of this composition in agriculture.
    CONTEXT
    Phytosanitary products can in principle be formulated in different ways, the properties of. active substances and the nature of the formula that may be problematic in terms of ease of preparation, stability and activity of the formulas. In addition, for economic and ecological reasons, some formulas are more advantageous than others.
    There is generally a need for formulas highly concentrated in active substances, since such formulas have a number of advantages. For example, the cost and complexity of packaging required are less than for low-concentration formulas. Consequently, there is a reduction in the cost and complexity of production, transport and storage, but the operations of preparation of the spraying liquids which are for example used in agriculture, are also simplified as a result of the handling of detrimental containers of phytosanitary products, such as during distribution and blending, for example.
    Unlike powder formulations, liquid formulas have the advantage of not producing dust when preparing a spray liquid which is usually done by adding water. Preferred liquid formulas, as they are concentrated, are concentrated suspensions. A concentrated suspension is defined as a suspension of solid particles of the active substance in a liquid to be diluted with water before use. Despite their ease of use, they are not as concentrated as powders for example. The liquid phase included in the formula, such as oil or water, is typically greater than half.
    The product development was aimed at obtaining fungicidal concentrated suspensions comprising as much active substance as possible. However, the degree of concentration is limited by the requirement to obtain a stable product, that is to say in which the solid particles do not settle (sedimentation) and which can be stored for a long period of time.
    Efforts are concentrated on reducing the size of the particle of the active substance. An increase in the area thus obtained is often correlated with greater chemical activity. Formulators have introduced surfactants into concentrated suspensions to improve the wetting properties and keep the active substance particles in suspension in the liquid phase.
    Dodecylguanidine acetate, known as dodine, is a fungicide recommended for control of a number of major fungal plant diseases. Dodine is presently formulated as wettable powders, concentrated suspensions and wettable granules. It is a slightly yellow powder with low solubility in water, particularly at 63 g / l at 25 ° C, and in organic solvents. H is used against scab of almond; scab of apple and pear trees; the Sigatoka disease of banana; anthracnose of the cherry tree; peacock eye disease of olive leaves; the peach screen, the peach blister; Sigatoka (early and late) of the peanut plant; peccary walnut scab, pecan walnut Gnomonia, brown and downy leaf spot, leaf blotch and downy mildew; and walnut anthracnose.
    Despite the importance of these active substances, the evolution in the field of concentrated suspensions comprising dodecylguanidine, or a salt, ester or a derivative thereof, has been limited. Stable concentrated suspensions of dodecylguanidine acetate typically comprise 400 grams of active ingredient per liter. This situation is unfavorable because the transport of products is expensive. This is certainly the case when the majority of the product is water. In order to reduce the environmental impact of such a formula, it would be advantageous to be able to produce formulas that are much more concentrated. It is also interesting to have formulas that have a better toxicological profile as long as they are sufficiently effective against the targeted pests.
    US 2008/274154 reports that concentrated suspensions containing a grafted acrylic copolymer surfactant and an alkoxylated ionic surfactant polyarylphenol phosphate ester are stable over time at high concentrations of active ingredients.
    US 2009/325808 discloses highly concentrated suspensions of slightly water-soluble pesticides that are protected from the "Ostwald Maturation" process by the use of polymeric surfactants. Also, EP 0 007 731 discloses that highly concentrated suspensions of phytosanitary active substances can be obtained using polymeric surfactants.
    WO 2009/082 939 discloses that highly concentrated suspensions of fungicides can be obtained by stabilizing an agrodimic active material with a nonionic dispersing agent and an anionic freezing agent. Dodine is one of the fungicides that can be formulated this way.
    The above information relates to anionic surfactants. This type of surfactant is not compatible with dodine.
    EP 0 388 239 discloses the use of so-called structured surfactants for the preparation of highly concentrated suspensions of agrochemicals or active biocides.
    None of this information describes concentrated suspensions of dodecylguanidine, its salts or derivatives having a concentration greater than 40%.
    There remains a need in the art for improved fungicidal concentrated suspensions comprising dodecylguanidine, or a salt, ester, or uqjleri thereof.
    The present invention aims to solve at least some of the problems mentioned above. The invention aims to provide a more concentrated formula than that which has been developed so far. The concentrated fungicidal suspension should be stable over long periods of storage. It must be economical. The ecological profile must be considered. Efficacy for the treatment of fungicidal diseases on agricultural crops should be maintained or improved.
    SUMMARY OF THE INVENTION
    The present invention relates to an aqueous concentrated suspension, as presented in claim 1, comprising as an active ingredient of the invention. dodecylguanidine, a salt or ester in the form of particles, characterized in that the median diameter of the particles (d50) is between 7 μm and 40 μm.
    By the term "aqueous" as used herein is meant that the solvent used in the composition is mainly water. Therefore, "aqueous" and "water-based" can be considered as synonyms. Water-based formulas generally have the advantage of requiring little or no organic solvent fraction.
    By the term "active" as used herein is meant an ingredient that is chemically active and / or biologically active at the origin. By the term "active ingredient" as used herein is meant dodecylguanidine or a salt, ester or a derivative thereof. With this in mind, an "active" ingredient can be a single ingredient or a combination of ingredients; and the meaning of the term "active" should be understood to include, but not limited to, dodecylguanidine or salt, ester or derivative thereof.
    Particle size is usually defined as a normal log distribution with a median diameter or d50 - of which ^ 50% of the measured particles are less than the median value and 50% are greater than the median value. The term "particle size distribution" as used herein refers to the relative percentages by weight or volume of each of different size fractions. The term "median particle size", "median particle diameter", "dso" / as used herein refers to the median or quantile 50% of a particle size distribution. The term "d50" therefore defines a size where 50 percent by volume of the particles have sizes smaller than the given value.
    Particle size distributions for the present application can be measured using laser light diffraction equipment, such as those sold by Malvern Instruments Ltd., Malvern, Worcestershire, United Kingdom. Other types of material are also suitable for particle size determinations. .
    Concentrated suspensions of dodecylguanidine or a salt, ester or derivative thereof, as known by all the skilled persons, generally have a median particle diameter of less than 5 microns, usually around 3 microns.
    The inventors have found to their greatest surprise that the increase in the diameter of the median particles has allowed the preparation of highly concentrated concentrated suspensions. These provide an economic benefit because savings can be made on transportation costs. The compositions provided by the invention are stable for long periods of time and are easy to use.
    In a second aspect, the present invention provides the use of a composition according to one embodiment of the invention for the treatment of a fungal disease on crops or ornamental plants, as described by claim 12.
    By the term "fungal disease" as used herein, a disease caused by a fungus is being eradicated. By the term "fungicide" as used herein is meant any toxin used to kill or inhibit fungal growth. In particular, the present invention relates to fungicides targeting fungi that cause damage to crops or ornamentals.
    The "fungal diseases" particularly targeted in the present invention are scab of almond; scab of apple and pear trees; the Sigatoka disease of banana; anthracnose of the cherry tree; the peacock eye disease of the olive leaves; the peach screen, the peach blister; Sigatoka (early and late) of the peanut plant; peccary walnut scab, pecan walnut Gnomonia, brown and downy leaf spot, leaf blotch and downy mildew; and walnut anthracnose.
    By the term "crops" or "crops" as used herein is meant any type of agricultural crop, including but not limited to cereals, rice, legumes, cotton, tobacco, vegetables and fruit plants. High-value crops are preferred over fruit crops, ornamental crops and nuts.
    Fruit crops include, for example, the fruits of the family Rosaceae, such as apple, pear, quince and; fruits, apricots, cherries, plums and peaches; berries, especially bramble fruits, such as blackberry, raspberry, blueberry and bramble, wild berries, such as blueberries and bilberries, other berries, such as gooseberry and blackberry; accessory fruits such as strawberries, fruits of the family Cucurbitacea, such as calabashes, including squash and pumpkins, melons and watermelons; citrus fruits and other subtropical fruits such as lemon, lime, grapefruit, mandarin, clementine, orange, avocado, guava, kumquat, logan, lychee and passion fruit, dates, figs, grapes, olives and pomegranates, and tropical fruits such as banana, coconut, durian, eggfruit, mango, mangosteen, papaya, pineapple and tamarind. .
    The favorite fruit plants are apple, cherry, olive, peach, and pear. Ornamental crops include, but are not limited to, aster, azalea, begonia, boxwood, cactus, caladium, calla, calendula, carnation, chrysanthemum, coleus, columbine, dahlia, daisy, daylily, delphinium, carnation , easter lily, fern, ficus, digitalis, fuchsia, gardenia, geranium, gerbera, gladiolus, hibiscus, impatiens, iris, ivy, marigold, nasturtium, thought, peony, petunia, phlox, roses, poinsettia, rosemary, rose, ficus, sage, sedum, snapdragon, verbena, periwinkle, wandering Jew and zinnia.
    The preferred ornamental crops are fern and rose.
    Walnuts include almonds, Brazil nuts, butternut, cashews, chestnuts, macadamia nuts, pecan nuts, peanuts, pistachios and walnuts.
    The favorite nuts are almonds, pecans, peanuts, and walnuts.
    The compositions provided by the invention are at least as effective as the compositions of the prior art when used in comparable doses per hectare. In particular, the effectiveness of the compositions provided by the invention for the treatment of fungal diseases on agricultural crops, and more particularly apple scab, is maintained or improved compared to suspension concentrates comprising 400 g / l of dodecylguanidine or salt, ester or a derivative. This was unexpected because we thought that the efficiency would decrease with a larger particle size due to a decrease in the contact area.
    DESCRIPTION OF THE FIGURES
    Figure 1 illustrates a typical particle size distribution of a solution of Dodine 544g / l SC according to one embodiment of the invention.
    Figure 2 provides a graphical representation of formulations where an average particle size is represented as a function of the viscosity of the resulting formulation.
    DETAILED DESCRIPTION OF THE INVENTION
    The present invention relates to an improved aqueous concentrate suspension, uses of the concentrated solution and a method of manufacturing the concentrated suspension.
    Unless otherwise indicated, all terms used in the disclosure of the invention, including technical and scientific terms, have the same meaning as commonly understood by one skilled in the art of this invention. Through new orientations, the definitions of terms * are included to better appreciate the teaching of the present invention.
    As used herein, the following terms have the following meanings "One", "one", and "the", "the", "the" refer to both the singular and the plural unless the context clearly explains the opposite. For example, "a compartment" refers to one or more compartments.
    "Approximate" as used herein referring to a measurable value such as a parameter, a quantity, a time duration, and the like, is intended to encompass the variation of +/- 20% or less, preferably +/- 10 % or less, more preferably +/- 5% or less, still more preferably +/- 1% or less, and still more preferably +/- 0.1% or less, of and from the specified value, to the extent that such variations are suitable for carrying out the disclosed invention.
    "Include", "include", "understands" and "composed of" as used herein are synonymous with "included", "including", "includes" or "containing", "containing", "contains" and is included or flexible terms that specify the presence of, for example, components and do not exclude or exclude the presence of other unlisted components, features, elements, members, steps, known in the art, or disclosed there.
    The enumeration of the numeric value ranges by the end points includes the numbers and fractions encompassed in this range, as well as the endpoints quoted.
    In a first aspect, the invention provides a concentrated aqueous suspension with a composition comprising, expressed by weight relative to the total weight of the composition: a) 40 to 80%, preferably 40 to 70%, the dodecylguanidine particles, a salt or ester, b) 0 to 10% of an anti-gel compound ec) 1 to 10% of a wetting agent and / or d) a dispersing agent, e) 0 to 5% of an antifoam agent f) It remains stable, characterized in that the median diameter of the particles (dso) is at least 7 μm and less than 40 μm.
    The term "aqueous concentrated suspension" refers to concentrated water-based suspensions.
    The expression "% by weight", here and elsewhere in the description unless otherwise indicated, refers to the relative weight of the respective component relative to the total weight of the formulation.
    The water fraction in the concentrated suspensions of the invention may be in general 20% -60% by weight, preferably 30% -45% by weight, more preferably 35% -40% by weight.
    The fraction of active ingredients (component a) in the concentrated suspensions is preferably 40% -80% by weight, in particular 45% to 60%, more preferably 50% to 55% by weight.
    In a preferred embodiment of the invention, the active ingredients (component a) are present with a minimum content of 400 g of active material / l, preferably 440 to 820 g of active material / l, more preferably 544 g of active ingredient / l of the overall formula.
    Suitable active ingredients for use in the invention are dodecylguanidine or a salt, ester or derivative, or a mixture thereof.
    By the term "dodecylguanidine, a salt or ester thereof" is meant an acidic salt of dodecylguanidine of the structure.
    Wherein X represents an acid residue of a mono carboxylic acid such as acetic, propionic, capric, stearic, benzoic, and naphthoic acid; the dicarboxylic acid as malonic or succinic and a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid or bisulphuric acid.
    According to a particularly preferred embodiment of the invention, the dodecylguanidine compound is a dodecylguanidine acetate, commonly known as dodine.
    According to a particularly preferred embodiment, the fungicidal concentrated suspension comprises dodine as an active ingredient, preferably in a concentration of 544 g / l.
    Dodine, 1-dodecylguanidinium acetate (dodecylguanidine mono acetate), is a registered fungicide and bactericide for use on pome fruits * stone fruits, including cherries, walnuts and walnuts .
    The concentrated suspensions of the invention are characterized in that 50% of the particles of the overall formulation, preferably 50% of the particles of the active ingredients (component a), have a size of at least 7 μm (d50> = 7 μm )
    Preferably 60%, more preferably 80% and even more preferably 90% of the particles of the entirety of the concentrated suspension have a size of at least 7 μm.
    According to a preferred embodiment, at most 2% of the particles have a size of at least 75 μm (d98)
    The upper limit is dictated by a spray nozzle as there is a risk of blocking them when there are too many particles of more than 40 pmL
    It is furthermore possible to add other formulation auxiliaries to these formulations, such as anti-freeze components, wetting agents, dispersing agents, defoamers, preservatives, or dyes.
    These formulation aids are for example described in Chemistry and Technology of Agrochemical Formulations, ed. D.A. Knowles, Kluwer Academic Publishers (1998) and Controlled - Release Delivery Systems for Pesticides, Herbert B. Scher, Marcel Dekker, Inc. (1999).
    The fraction of these formulation auxiliaries in the concentrated suspensions of the invention is preferably 0-30% by weight, in particular 2% -15% by weight, preferably 5% -10% by weight.
    According to a preferred embodiment of the invention, the anti-gel component (component b) is selected from the list of glycols, glycerols, urea and mixtures thereof.
    According to a preferred embodiment, the antifreeze compound (component b) is a glycol selected from the list of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, and mixtures thereof.
    According to a particularly preferred embodiment, the anti-freeze compound is propylene glycol.
    The term "surfactant", which includes the terms "emulsifiers" and "detergents" as used herein, means the composition of matter that either alters the surface tension when dissolved in water or an aqueous solution. or modifies the interfacial tension between immiscible liquids or a liquid and a solid.
    Suitable agents for the purposes of the present invention are listed in McCutcheon's Emulsifiers & Detergents, at 287-310 of the North American Edition (1994), and in McCutcheon's Emulsifiers & Detergents, at pages 257-278 and 280 of the International Edition (1994), both published by MC Publishing Co. (McCutcheon Division) of Glen Rock, NJ.
    In this regard, suitable surfactants include, but are not limited to, ethoxylated alkylamines, ethoxylated grafted ethoxylated graft copolymers, ethoxylated alcohol or carboxyl alkylphenol ethoxylated block copolymers, ethoxylated alcohols, ethoxylated alkylphenols, glycol, polyethylene glycols, silicone surfactants, and ethoxylated tristyrylphenol.
    In a preferred embodiment, the surfactant is an acrylate graft copolymer. An example of acrylate graft copolymer is Tersperse 2005 (Huntsman). This surfactant is readily soluble in water and acts as a dispersant.
    Preferred surfactants are selected from the group consisting of wetting agents, dispersing agents, and mixtures thereof.
    The wetting agents serve to reduce the surface tension at the water-solids interface and consequently to increase the tendency of the water to be in contact with the total surface of the active ingredient particles.
    According to a preferred embodiment of the invention, the wetting agent (component c) is an ethoxylated alcohol. According to a particularly preferred embodiment of the invention, the wetting agent (component C) is chosen from the list of ethoxylated alkylphenols, ethoxylated alkylamines, ethoxylated alcohols and ethoxylated tristyrylphenol.
    In a preferred embodiment, the wetting agent (component c) is an ethoxylated alkylamine. Examples of ethoxylated alkylamine wetting agents (component c) are R6dhamene "RAM 7" (Rhodia) or EmulsorT AG / NflT (Cesalpina) .The advantage of this surfactant is that it acts as a wetting / dispersing agent and shows a degree of high compatibility with the dodine. '
    In another preferred embodiment, the wetting agent (component c) is an ethoxylated alcohol. The ethoxylated alcohols are prepared from saturated or unsaturated, linear or branched aliphatic alcohols having an average of 8 to 20 carbon atoms and which contain from 5 to 25, typically from 10 to 20 ethylene oxide units per molecule.
    Ethoxylated alcohols are preferred, containing from 12 to 18 carbon atoms in the alcohol portion and 10 to 20 ethylene oxide units.
    Examples of ethoxylated alcohols are Brij, Volpo, Arlasolve, Atphos, Synperonic and Lubrol, Synperonic 91-6, Atplus MBA 11-7 (Unigema). .
    Examples of ethoxylated tristyrylphenol wetting agents (component c) are Soprophor® 3D33 (= tristyrylphenol ethoxylated with 16 EO and phosphated), Soprophor® BSU (= tristyrylphenol ethoxylated with 16 EO), Soprophor® CY / 8 (Rhodia) (= tristyrylphenol). ethoxylated with 20. EO), and Hoe® S3474 (= tristyrylphenol ethoxylated with EO) and as Sapogenat® T (Clariant), such as Sapogenate T 100 (= triisobutylphenol ethoxylated with 10 EO), for example.
    The fraction of surfactants in the concentrated suspension of the invention is generally 0% -10% by weight, preferably 1% -5%, more preferably 2% -4% by weight and still more preferably about 3% by weight.
    According to a preferred embodiment of the invention, the proportion of wetting agent relative to the dodecylgyuanidine particles, a salt, an ester or a derivative is between 1/8 and 1/80, preferably between 1/10 and 1/25, and more preferably between 0.04 and 0.06.
    The term "dispersant" or "dispersing agent" as used herein refers to a surfactant that is added to the suspending medium to promote uniform suspension or separation of solid particles, often of micron size.
    Dispersants (component b) suitable for the purposes of the present invention are listed in McCutcheon's Functional Materials, at pages 122-142 of the North American edition (1994), as well as in McCutcheon's Functional Materials, at pages 47-56 of the US Pat. International Edition (1994), both published by MC Publishing Company (McCutcheon Division) of Glen Rock, NJ.
    In this regard, suitable dispersants include, but are not limited to, acrylate graft copolymers. Examples of dispersant (component c) are Tresperse 2500 (Huntsman).
    The term "defoaming agent" or "anti-foaming agent / ingredient" should be understood as a substance used to reduce foaming. Foaming can result from the presence of foam inducing agents such as proteins, gases or nitrogenous materials. The presence of. Foam is usually undesirable because it can interfere with the treatment.
    Antifoam agents are generally discussed on pages 430-447 of Kirk-Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, published in 1979 by John Wiley & Sons, Inc.
    Suitable antifoaming agents (component e) for purposes of the present invention include, but are not limited to, silicone-based defoamers of Wacker, Rhodia or Dow Corning, for example; acetylene-based defoamers such as those of Air Products for example, and perfluoroalkylphosphinic acid and phosphonic acids and their salts.
    The preferred antifoams are those of the group of polydimethyloxanes having a molar dynamic viscosity mored at 25.degree. C., ranging from 1000 to 800 mPa.s, usually 1200 to 6000 mPa.s and containing silica. Silica includes polysilicic acids, metasilicic acids, ortho-silicic acids, silica gels, silicic acid gels, kieselguhr, precipitated SiO 2 and the like.
    The antifoams of the liner polydimethylsiloxane group have, as chemical backbone, a compound of the formula Si (CH 3) 2 -O-] nH, in which the last groups are modified, for example by etherification, or are attached to the -Si group ( CH3) 3. Examples of antifoams of this kind are Rhodorsii® Antifoam 416. Other suitable defoamers are Rhodorsil® 1824, Antimussol 4459-2 (Clariant, Defoamer V4459 (Clariant), SE Visk and AS EM SE 39 (Wacker).
    Especially preferred are polydimethylsiloxanes wherein two methyl groups are attached to each silicone atom to form (H3C) [SiO (CH3) 2] nSi (CH3) and simethicone, which is a mixture of poly (diethylsiloxane) and silica.
    An example of an appropriate antifoam is Rhodorsil® 481 and Rhodorsil® 454 (polydimethylsiloxane and Silicon) from Rhodia.
    An aqueous concentrated suspension according to one embodiment of the invention may further comprise g), a thickening agent and / or h), a biocidal compound.
    A suitable thickening agent (component g) is a hydroxyethylcellulose, a gelling and thickening agent derived from cellulose.
    Hydroxyethylcellulose surface-treated with glyoxal is particularly preferred. A suitable thickener is, for example, IMatrosol® 250 HXR from Hercules-Aqualon. 'v
    Suitable preservatives (component h) are typical biocidal compounds, an example being Promex Na20S (1,2-Benzisothiazolin-3-one) from Prom Chem, and Acticide® MBS (1,2-benzoisothiazol-3 (2H) mixture). -one and 2-methyl-2H-isothiazol-3-one, biocide) from Thior.
    In a preferred embodiment of the invention, the concentrated suspension further comprises g), a thickening agent and / or h), a biocidal compound in a concentration of up to 1%, expressed by weight relative to total weight of the composition.
    In a preferred embodiment of the invention, the spraying continues until 50% of the particles of the active ingredient, of technical quality, have a size of at least 8 μm (d50> = 8 μm). preferably at least 10 μm, more preferably at least 11 μm.
    Preferably in this case, at least 60% of the active material particles (component a) in the formula have a particle size of d 50 of at least 7 μm, more preferably 70% and even more preferably 80% of the principle particles. active have a particle size of at least 7 μm.
    In one embodiment of the invention, the median particle diameter of the active ingredient is at least 10 μm, preferably at least 12 μm, more preferably at least 14 μm, and more preferably at least 12 μm. about 15 pm.
    In a preferred embodiment of the invention, the viscosity of the concentrated suspension is between 500 and 1000 mPa.s (cps), preferably between 600 and 900 mPa.s (cps), more preferably between 700 and 800 mPa. s (cps) and even more preferably around 750 mPa.s (cps).
    In a preferred embodiment of the invention, the concentrated suspension comprises (expressed by weight relative to the total weight of the composition): a) from 45% to 60% by weight of dddecylguanidine or uhsel, a derived ester, b) 1 to 5% of an anti-freeze compound, c) Γ 5% of a wetting agent, d) up to 2% of a dispersing agent, e) up to 2% of an antifoaming agent, and f) the rest of the water.
    In a preferred embodiment of the invention, the concentrated suspension comprises (expressed by weight relative to the total weight of the composition): a) 50 to 55% of dodecylguanidine particles or a salt, an ester or a derivative, b) 3% of an anti-freeze compound, c) 3% of a wetting agent, d) 1% of a dispersing agent, e) 1% of an anti-foaming agent, g) 0.1% thickener, h) 0.1% of a biocide, and the rest of water.
    With the concentrated suspension of the invention, it is generally possible to obtain an equal or greater biological effect for the same application rate. Due to a larger particle size than conventional formulations, the formulation may be less toxic to lumens.
    In addition, the high concentration formulation of active ingredients in the concentrated suspension of the invention provides related benefits, such as a reduction in packaging, as a result of which the cost and complexity associated with the production, transportation and Storage is reduced and the preparation of spray mats used in agriculture can be managed more efficiently with smaller quantities, such as in distribution operations and mixing preparations, for example.
    The concentrated suspension of the invention additionally exhibits excellent dispersion and stabilizing properties after further dilution with liquids, preferably water.
    Thirdly, the concentrated suspension of the invention produces formulations which are storage stable (for long periods).
    The invention also provides compositions obtainable from a dilution of the concentrated suspension of the invention with liquids, preferably aqueous liquids and even more preferably water.
    It may be advantageous to add other active components to the compositions thus obtained, preferably active agrochemical ingredients (for example, extemporaneous mixing partner formulations and / or auxiliaries and additives customary for the application, examples being the self-emulsifiable oils such as vegetable oils, or liquid paraffins and / or fertilizers The present invention accordingly provides other compositions of this kind, preferably fungicidal compositions, which are based on the concentrated suspension of the 'invention.
    In a third aspect, the invention provides uses of a concentrated suspension in the integration of the invention to the treatment of a fungal disease on agricultural crops.
    In a preferred embodiment, a concentrated suspension, according to an application of the invention, is used for the treatment of apple scab.
    Scab, caused by the pathogenic fungus Venturia inaequalis, is considered to be the most important apple disease worldwide and one of the most expensive to control. .
    In the efficacy test, the treatment of apple scab with Dodine 54'4'SC 'was compared with "Syllit® 400 SC," a "commercially available product" containing 400g / l deodin , and for many crops, Dodine 544 SC was significantly more effective than Syllit® 400 SC.
    In a fourth aspect, the invention provides a method for treating an agricultural crop, comprising a step of diluting an aqueous concentrated slurry according to an integration of the invention and applying to the crop an effective amount of the concentrated diluted suspension.
    By the term " effective amount " as used herein is meant the minimum amount of the active ingredient needed to control the fungal disease of interest.
    In a preferred embodiment, about 1.25 liters of an aqueous concentrated suspension according to the invention are dissolved in 400 liters of water to prepare a composition for the treatment of 1 ha.
    In spite of the increased particle size of the active ingredient, which was thought to be detrimental to the biological activity of the spraying liquid, a composition according to the invention, and more particularly Dodine 544 SC (concentrated suspension comprising 544g / l dodine), was at least as effective as Syllit® 400 SC (suspension concentrate comprising 400g / l of dodine).
    The concentrated suspensions of the invention are produced in a known manner (see Winnackef-Küchler, "Chemische Technologie", volume 7, C. Hanser Verlag Munich, 4 January 1986), as wet grinding of the components. for example, which can take place in suitable grinders, such as in ball mills, (such as the continuous Bead Mills of Drais or continuous Bead Mills of Bachofen for example), or in the Colloids
    Mills (like the dented colloid mills of Probst + Claasen, for example).
    Concentrated suspensions described in the art are generally prepared by wet milling. By the term "wet grinding", in this invention, the milling of materials in water or other liquid.
    The active ingredient in particulate form is usually wet-milled until the particle diameter of the active ingredient reaches a diameter of about 3 μm. The formulation then has a viscosity of about 1000 mPa.s (cps).
    Unexpectedly, the concentrated suspensions containing unusually large particles compared to the concentrated suspensions seen in the art of dodecylguanidine, have remained stable over extended periods of time.
    According to a preferred embodiment, a concentrated suspension, according to the integration of the invention, will be stable during storage at a temperature of 25 ° C. for a period of at least 6 months, preferably 12 months, more preferably 16 months and even more preferably 24 months. In a better integration, a concentrated suspension of the invention has a storage stability of at least one year. Storage stability can be measured using techniques known to a skilled person.
    For a quick indication of the extended storage stability of a product, the CIPAC MT 46 accelerated heating test method can be used. Several parameters are usually analyzed before and after heating and compared to determine if the products have changed. pH (CIPAC MT 75.3), discharge (CIPAC MT 148.1), suspension (CIPAC MT 184) / spontaneity of dispersion (CIPAC MT 160), wet sieve test (CIPAC MT 185), persistent foam (CIPAC MT 47.2 ), particle size distribution (CIPAC MT 187), low temperature stability (CIPAC MT 39.3).
    The content of the active ingredient can be measured by analytical methods which are understood by one of ordinary skill in the art. The surface is dodine ~ ~ ~ exe ~ mple, 'small be determined by reverse phase HPLC using an ODS-2 column of 250 x 4.6 mm (eg Inertsil 5 ODS-2, a particle size of 5 pm or equivalent) with a mobile phase composed of acetonitrile and water with 0.005 M heptane sulfonic acid pH 3.5 (H3PO4) and UV detection at 200 nm. Standardization is done by external calibration.
    According to a preferred embodiment of a process of the invention, more than 450 g, preferably greater than 500 g of dodecylguanidine or one of its salts or esters, expressed per liter of the concentrate, have been suspended.
    According to a preferred embodiment of a process of the invention, at least 500 g / l of dodecylguanidine or a salt, an ester or a derivative, expressed per liter of the concentrate, are suspended from the composition.
    According to a preferred embodiment of a method of the invention, the method further comprises the step of adding in a quantity of a thickener to the concentrated suspension to obtain a viscosity of between 500 and 1000 mPa.s ( cps), preferably around 750 mPa.s (cps).
    The invention is described in more detail in the following nonlimiting examples which illustrate the invention, and which are not intended to limit the scope of the invention and should not be interpreted in this way.
    The present invention will now be discussed in more detail with reference to non-limiting examples.
    It is believed that the present invention is not limited to any of the above-described embodiments and that certain modifications may be added to the example of manufacture shown without questioning the appended claims. For example, the present invention has been described with reference to dodecylguanidine acetate, but it is clear that the invention can be applied to dodecylguanidine salts for example or mixtures of dodecylguanidine acetate with other active ingredients. .
    EXAMPLES
    Example 1 Preparation of Dodine 544 SC
    The water was introduced into a container. Formulation additives, in particular propylene glycol (antifreeze agent), ethoxylated alkylamine (wetting agent), acrylic graft polymers (dispersing agent), silicon oil (anti-foaming agent) and 1,2- Benzisothiazolin-3-one (preservative) was added according to the recipe shown in Table 1. The active ingredient was suspended in the aqueous mixture.
    Hydroxyethylcellulose (thickener) was added until a viscosity of about 750 mPa.s (cps) was obtained. The particle size distribution of the mixture was measured using a particle analyzer. The data for 544 SC dodine were as follows: mean: 11.08 μm, standard deviation: 9.015 μm, median: 7.837 μm, variance: 81.27 pm2, HP: 81.3%, mode: 5.354 μm, <10% : 2.634 μm, <25%: 4.551 μm, <50%: 7.837 μm, <75% 15.22 μm, <90% 24.09 μm.
    Table 1: Dodine 544 SC
    Example 2 Storage Stability of 544 SC Dodine
    An accelerated storage stability test according to the CIPAC MT 46 method was performed on samples obtained from the product described in Example 1. The results obtained for a set of parameters are listed in Table 2. As we can , see in the results, the concentrated suspension has remained stable, according to one embodiment of the invention.
    Example 3: Efficacy data for dodine 544 SC Brief description of the experiment
    Fungicides were applied with a fogger from late March 2010 to mid-June 2010. The experiment was configured as a random block of 12 treatments and 4 replicates. The evaluations were made according to the guidelines EPPO PP 152/3 "Design and Analysis of Biological Evaluation Tests, PP 1/135 (3) Evaluation of Phytotoxicity", PP 1/182 (3) "Conduct and presentation of tests biological evaluation, including GEP ", PP 1/5 (3)" Venturia inaequalis and V. Pyrina, CEB 14 apple and pear scab "; on infections of shoots, fruits and leaves. New fungicide formulations have been compared to standards and control (untreated) treatment.
    Orchard and equipment The experiment was carried out on a test site in Greece. The trial site is an orchard with varieties of apple (Malus domestica, the Pink Lady variety). The treatments were applied with a mist at a speed of 0.18 km / h. This results in a volume of pulverization of 1000 liters / hr.
    Table 2: Storage stability of the concentrated aqueous suspension obtained in Example 2.
    Treatments 9
    The following fungicides have been applied: a. Not treated b. Dodine 544 SC 0.125 1/100 I 680g of ingredient attic / ha c. Syllit® 400 SC 0.170 1/100 I 680g of active ingredient / ha Results
    The preliminary results are presented in Table 3. In this table, the averages followed by the same letter do not vary significantly (P = 0.05, Student-Newman-Keuls). From the results, it can be concluded that 544 SC dodine formulation controls scab on apples in a way that is at least equivalent and even better than Syllit® 400 SC.
    Table 3: Results of the field experiment

    '
    Example 4:
    Several 600 SC dodine formulations were prepared according to the compositions described in Table 4. The average particle size d50 (μm) was determined as a function of the viscosity of the composition, as shown in FIG. FIG. 2 shows that the viscosity increases progressively from about 150 mPa.s to more than 3000 mPa.s for an average particle size of 4 and less. Such viscosity is undesirable because the formulation becomes too viscous and therefore difficult to handle. It is preferable that the viscosity of a SC formulation be in the range 550 rpm to 1050 mPa.s, and it is even more preferable that it be around 800 mPa.s. This value is obtained for an average particle size of 7 μm.
    Table 4: Dreoaration of dodine formulations fic
    权利要求:
    Claims (12)
    [1]
    1. A concentrated suspension composition contains, expressed by weight relative to the total weight of the composition: a) 40 to 80%, preferably 40 to 70%, dodecylguanidine particles, a salt, an ester or a derivative, b ) 0 to 10% of an anti-freeze compound, c) 1 to 10% of a wetting agent and / or d) a dispersing agent, e) 0 to 5% of an anti-foaming agent, f) the remaining water, characterized in that the median particle diameter (d50) is at least 7 μm and less than 40 μm.
    [2]
    . The concentrated suspension of claim 1 having a composition wherein the average particle diameter is at least 10 μm and preferably about 15 μm.
    [3]
    3. Concentrated suspension according to claim 1 or 2, comprising a dodecylguanidine ester or a dodecylguanidine acetate (dodine).
    [4]
    4. Concentrated suspension according to one of claims 1 to 3, with a viscosity of between 500 and 1000 mPa.s (cps), preferably around 750 mPa.s (cps).
    [5]
    5. concentrated suspension according to one of claims 1 to 4, comprising, expressed by weight relative to the total weight of the composition: a) 45 to 60% of dodecylguanidine particles, a salt, an ester or a derivative,. b) 1 to 5% of an anti-freezing compound, c) 1 to 5% of the less-active agent, d) up to 2% of a dispersing agent, e) up to 2% of an antifoaming agent, and f) the remainder of water.
    [6]
    6. concentrated suspension according to one of claims 1 to 5, further comprising a thickening agent and / or a biocidal compound in a concentration of up to 1%, expressed by weight relative to the total weight of the composition.
    [7]
    7. concentrated suspension according to one of claims 1 to 6, comprising, expressed by weight relative to the total weight of the composition: a) 50 to 55% of dodecylguanidine particles, a salt, an ester or a derivative, b) 3% of an anti-freeze compound, c) 3% of a wetting agent, d) 1% of a dispersing agent, e) 1% of an anti-foaming agent, g) 0.1% of a thickener , h) 0.1% of a biocide, and f) the rest of the water.
    [8]
    8. Concentrated suspension according to one of claims 1 to 7, wherein the anti-freeze compound is selected from the list of propylene glycol, urea, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol; preferably propylene glycol.
    [9]
    The concentrated suspension according to one of claims 1 to 8, wherein the antifoam is a silicone oil, a perfluoroalkylphosphinic acid or a salt thereof.
    [10]
    The concentrated suspension according to one of claims 1 to 9, wherein the wetting agent is selected from the list of ethoxylated alkyl amines, acrylate graft copolymers, ethoxylated alkyl phenols, ethoxylated alcohols, and ethoxylated tristyrylphenols, preferably acrylate graft copolymers.
    [11]
    11. Concentrated suspension according to claim 10, wherein the proportion of wetting agent relative to the dodecylguanidine particles, a salt or an ester thereof, is between 1/8 and 1/80, preferably between 1/10 and 1/80. and 1/25, and even more preferably between. 0.04 and 0.06.
    [12]
    12. Use of a concentrated suspension according to one of claims 1 to 11 for the treatment of a fungal disease on crops or ornamental plants; preferably for the treatment of scab on apple trees.
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    HRP20140353T1|2014-07-04|
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    法律状态:
    优先权:
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    PCT/EP2011/064397|WO2013026470A1|2011-08-22|2011-08-22|Aqueous suspension concentrate comprising dodecylguanidine|
    EP2011064397|2011-08-22|
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