Herbicidal formulations based on essential oils

Abstract

The present invention relates to herbicidal formulations that are non-selective against broadleaf and narrow-leaf weeds, suitable for emulsification in water before use, and methods for preparing same. The formulations comprise: cinnamon essential oil, rosemary essential oil, clove essential oil and geranium essential oil; a vegetable oil selected from coconut oil, palm kernel oil and mixtures of same; an emulsifying additive derived from ethoxylated sorbitan esterified with fatty acids; an adhesion-improving additive based on paraffin mineral oils; and an agent for protecting against light that includes benzophenone in an amount that provides at least 200 mg benzophenone per litre of herbicidal formulation. The invention also relates to herbicidal compositions in the form of an aqueous emulsion, methods for preparing same, and methods for controlling weeds that include applying the herbicidal compositions in the form of an aqueous emulsion. The herbicidal formulations and compositions of the invention are biodegradable, environmentally biocompatible, free of synthetic herbicides and capable of reducing or minimising the degradation of the essential oils resulting from conditions of sunlight and heat.

Description

[0001] HERBICIDE FORMULATIONS BASED ON ESSENTIAL OILS Technical field of the invention

[0002] The present invention relates to herbicidal formulations with natural components, and in particular, to formulations with extended non-selective herbicidal activity based on essential oils, with protective capacity against light and heat of the compounds with herbicidal activity within said essential oils, and adjuvant compounds for the control or eradication of weeds.

[0003] Background of the Invention

[0004] Weeds, also known as invasive plants, are all unwanted plants with no economic value that grow in an agricultural ecosystem, competing for water, nutrients, space, and light with the desired plants of economic value. Weeds, along with pests and bacterial and viral diseases, are among the main biological threats to crops. It is estimated that in developing countries, weeds cause the annual loss of approximately 125 million tons of food, enough to feed 250 million people (Parker C. & J. Fryer. 1975. Weed control problems causing major reduction in world food supplies. FAO Plant Protection Bulletin 23 (3 / 4): 83-95).

[0005] In this regard, the industry has provided synthetic compounds for combating pests, diseases, and weeds, which have demonstrated both their effectiveness and their persistence and presence in food and agricultural soil. Synthetic herbicides are frequently associated with various human health problems, including allergies and cancer. Likewise, these agricultural herbicides also appear to cause harm to beneficial flora, fauna, and microbiota in the environment, among other harmful effects.

[0006] Some more natural and ecological alternatives have been tested to replace synthetic herbicides. Substances such as vinegar (diluted acetic acid), urea, urine, ammonium nitrate, and essential oils are often used as organic herbicides. In particular, essential oils contain substances with allelochemical properties (commonly called allelopathic substances) that inhibit or affect weed growth, both in the plant form and in seed germination, which has been extensively studied. Likewise, the use of essential oils for weed control is also well-established in the prior art. For example, Tworkoski conducted tests with twenty plant oils and their herbicidal effects on weeds, specifically on dandelion (Taraxacum officinale) (Tworkoski, T. Herbicide effects of essential oils. Weed Science, 50: 425-431. 2002).

[0007] The combination of two or more essential oils for weed control is also known. For example, US patent application 2021 / 251218 A1, assigned to the University of Liège, describes herbicidal compositions in emulsion form that include at least one essential oil as the active component, at least one surfactant, at least one oily substance from the vegetable oil group, and water. The essential oils used in this document are cinnamon oil (various species of the genus Cinnamomum), citronella essential oil (Cymbopogon winterianus and C. flexuosus), lemon essential oil, and eucalyptus essential oil (various species of the genus Eucalyptus).

[0008] Another document that also refers to an environmentally friendly herbicide is that of US patent 5,035,741, assigned to Safer, Inc., in which a herbicidal composition is disclosed that includes an effective herbicidal amount of a monocarboxylic fatty acid component in the form of two or more fatty acids selected from caprylic acid, pelargonic acid, capric acid, undecanoic acid and lauric acid, an emulsifier and an oil component selected from triglycerides, represented by some vegetable oils, terpenoids, in the form of pine oil, eucalyptus oil, orange oil and cedar oil, and paraffinic mineral oils.

[0009] Some weed control products based on essential oils are well-known and widely marketed. For example, GreenMatch® and Avenger Weed Killer®, which contain d-limonene, Matratec®, with clove oil, WeedZap®, which includes clove and cinnamon oils, and GreenMatch EX® with lemongrass oil, are some of the best-known commercial herbicides.

[0010] Combinations of synthetic pesticide compounds, including those exhibiting herbicidal activity, with essential oils have also been proposed to provide formulations with combined or complementary effects from both types of components. An example of this is U.S. patent application US 2020 / 345004 A1, assigned to Ingevity South Carolina, LLC, which describes a formulation suitable for agricultural use that includes an active component selected from a pesticide, fungicide, herbicide, or mixtures thereof, a natural oily solvent, and a nonionic surfactant. The natural oily solvent can be selected from long-chain fatty acid esters, including vegetable oils.

[0011] Even though essential oils exhibit herbicidal activity against weeds, they present a critical problem that has not been satisfactorily resolved. In their review study, Turek, C. and Stintzing, FC confirm this, namely, that when essential oils are exposed to sunlight, heat, and oxygen, several of their components can be degraded, altering their structure and causing them to lose desirable properties (Turek, C. & Stintzing, FC Stability of essential oils: A review. Comprehensive reviews in food science and food safety, 2013, vol. 12, no. 1, pp. 40-53).Therefore, any formulation that includes essential oils, for example, those in documents US 2021 / 251218 Al, US 5,035,741 and US 2020 / 345004 Al, as well as the commercial herbicide products based on essential oils mentioned above, will always have photochemical stability problems with respect to the components of said essential oils under the factors mentioned, the most important being the UV light from the sun to which they will be exposed after application in the field to the weeds, as well as the temperature at which said weeds are found in the field, which is usually considerably higher than the typical ambient temperature (25 °C), for example, at least 30°C.

[0012] Another problem that herbicide formulations based on essential oils generally present is their selective herbicidal capacity; that is, they are only able to act on a limited group of weeds, or even only on a specific weed. While US patent 5,035,741 indicates that its herbicidal formulations are non-selective, this does not mean that its composition is the only one that can achieve this effect. In fact, the composition of US patent 5,035,741 has quite specific technical characteristics for its components, so to achieve the non-selective capacity of said composition, it was necessary to use precise and specific compounds.

[0013] Furthermore, the presence of synthetic herbicides in herbicide formulations that include essential oils, as occurs in the formulations of document US 2020 / 345004 Al, makes these herbicide formulations not fully biodegradable and, therefore, not environmentally friendly, because these synthetic herbicides almost always cause harmful effects in the cycles of agricultural soil or bodies of water where they may permeate, even affecting other organisms present in them.

[0014] Therefore, there is a need to provide herbicide formulations based on essential oils that include components that are biodegradable and biocompatible with the environment and that are free of synthetic herbicides, with the capacity to reduce or minimize their degradation due to the effects of sunlight and heat related to their application in the field, as well as having a non-selective herbicidal effect to act on a large number of weeds, both broadleaf and narrowleaf, resulting from a specific combination of essential oils and other environmentally friendly components in specific quantities, thus solving in a unified way the technical problems raised above and which the state of the art has not yet been able to solve satisfactorily as a whole.as well as the appreciation of other advantages derived from solving these technical problems for a person trained in the technique.

[0015] Summary of the Invention

[0016] An objective of the present invention is to provide a herbicide formulation based on essential oils, biodegradable and biocompatible with the environment and free of synthetic herbicides.

[0017] Another objective of the present invention is to provide a herbicide formulation based on essential oils, which has the ability to reduce or minimize their degradation due to sunlight and heat conditions in the field.

[0018] Another objective of the present invention is to provide a herbicidal formulation based on essential oils, with a non-selective herbicidal effect on weeds, whether broadleaf or narrowleaf.

[0019] In another objective of the present invention, a herbicidal composition in the form of an aqueous emulsion ready for application on one or more target weeds is provided, which includes a herbicidal formulation based on essential oils of the present invention.

[0020] In yet another objective of the present invention, a method is provided for preparing a herbicide formulation based on essential oils.

[0021] In another objective of the present invention, a method is provided for the non-selective control or eradication of weeds by applying a herbicidal composition in the form of an aqueous emulsion, which includes a herbicidal formulation based on essential oils of the present invention.

[0022] Detailed Description of the Invention

[0023] In accordance with the foregoing, it should be understood that the objectives of the invention correspond to general or exemplary modalities in the broadest sense thereof, so it will be evident that changes, alternatives, combinations, variations and substitutions may be applicable, providing additional modalities of the invention that is the subject of this document, which will be both described below and easily deducible for a person skilled in the art, without this representing teachings beyond what is established in the present invention.

[0024] According to at least one objective of the invention, it relates, in general, to a non-selective herbicide formulation suitable for emulsification in water prior to use, comprising a plurality of essential oils, a vegetable oil, an emulsifying additive, an adhesion-enhancing additive, and a light-protecting agent.

[0025] The selection of the plurality of essential oils is one of the keys to contributing to the superior non-selective herbicidal effect of the formulations of the present invention for the control of both broadleaf and narrowleaf weeds. The inventors found that the presence of four specific principal essential oils, in conjunction with the other components, provides a non-selective herbicidal effect far superior to that provided by any other combination of essential oils. For the present invention, these specific principal essential oils useful for the invention are cinnamon essential oil, rosemary essential oil, clove essential oil, and geranium essential oil.

[0026] Cinnamon essential oil includes one or more essential oils obtained from plants of the genus Cinnamomum recognized as useful for obtaining essential oils with herbicidal activity. Specifically, cinnamon essential oil obtained from the Cinnamomum verum plant, extracted primarily from the leaves, bark, and raspberries by known methods, is preferred for inclusion as cinnamon essential oil, either as the sole cinnamon essential oil in the herbicide formulation or in a major proportion (>50% by volume) within a mixture of cinnamon essential oils with plants of other species of the genus Cinnamomum. Also preferably, the extraction of the cinnamon essential oil is carried out by processes that include alcoholic or hydroalcoholic extraction steps and low-pressure distillation. The herbicide formulations of the present invention include cinnamon oil in a proportion of 27.0% to 33% by volume.0% by volume, with respect to the total volume of the herbicide formulation.

[0027] With regard to rosemary essential oil, this includes those essential oils obtained from the plant Salvia rosmarinas, also known as Rosmarinus officinalis. This rosemary essential oil is obtained primarily from the stems and leaves of the plant using known methods. Preferably, the extraction of rosemary essential oil is carried out by supercritical fluid extraction with alcoholic cosolvents. The herbicide formulations of the present invention include rosemary oil in a proportion of 9.0% to 11.0% by volume, relative to the total volume of the herbicide formulation.

[0028] Furthermore, the clove essential oil useful for the invention is obtained from the plant Syzygium aromaticum, also known as Eugenia caryophyllus, where said essential oil is obtained primarily from the leaves and flowers, by known methods. Preferably, the extraction of the clove essential oil is carried out by processes that include stages of alcoholic or hydroalcoholic extraction and low-pressure distillation. The herbicide formulations of the present invention include clove oil in a proportion of 13.0% to 17.0% by volume, with respect to the total volume of the herbicide formulation.

[0029] Geranium essential oil includes one or more essential oils obtained from plants of the genus Pelargonium recognized as useful for obtaining essential oils with herbicidal activity. In particular, geranium essential oil obtained from Pelargonium hortorum, known as garden geranium, or Pelargonium graveolens, known as bourbon geranium, extracted primarily from leaves, flowers, and stems by known methods, is preferred for inclusion as geranium essential oil, either alone or in mixtures thereof. Also preferably, the extraction of geranium essential oil is carried out by processes that include alcoholic or hydroalcoholic extraction steps and low-pressure distillation. The herbicide formulations of the present invention include geranium oil in a proportion of 4.0% to 6.0% by volume, with respect to the total volume of the herbicide formulation.

[0030] With respect to the vegetable oil, conveniently for the invention, it may be any vegetable oil with a lauric acid content of at least 30% by weight of the total vegetable oil. Preferably, the vegetable oil may be coconut oil, palm kernel oil, or mixtures thereof, with coconut oil being more preferred as the sole vegetable oil or as the major component (>50% by volume) of mixtures that include it. The vegetable oil serves, among other functions, to dissolve the outer waxy layer of the weeds, allowing the allelopathic compounds that constitute the essential oils to penetrate the layers beneath the outer waxy layer and exert their herbicidal activity. Furthermore, the vegetable oil helps protect the essential oils from heat and volatilization, thereby allowing a greater quantity of these essential oils to remain in contact with one or more target weeds for a longer period of time.The herbicide formulations of the present invention include vegetable oil in a proportion of 27.0% by volume to 33.0% by volume, with respect to the total volume of the herbicide formulation.

[0031] The emulsifying additive is a non-ionic surfactant with an HLB of 8 to 16, which is preferably an ethoxylated sorbitan derivative esterified with fatty acids, such as polysorbate 20 (polyoxyethylene (20) sorbitan monolaurate), polysorbate 40 (polyoxyethylene (20) sorbitan monopalmitate), polysorbate 60 (polyoxyethylene (20) sorbitan monostearate), polysorbate 65 (polyoxyethylene (20) sorbitan tristearate), polysorbate 80 (polyoxyethylene (20) sorbitan monooleate), and any mixture of two or more of the same, polysorbate 80 being the preferred emulsifying additive for carrying out the invention. These compounds are found under the name Tween (Tween 20, Tween 40, etc.).Polysorbates, as emulsifying additives, have the primary functions of improving the homogenization of all the oily components that make up the herbicide formulations of the present invention, including those that may contain a certain amount of water, in which case the herbicide formulations of the present invention can be considered as water-in-oil emulsions; enabling the formation of emulsions of said herbicide formulations with water, to form herbicide compositions in the form of an aqueous emulsion ready for field application on one or more target weeds of the present invention; and contributing, together with the adhesion enhancer additive, to make the contact and adhesion of the oily components to the one or more target weeds more effective. Preferably, the herbicide formulations of the present invention include the emulsifying additive in a proportion of 1.0% by volume to 5.0% by volume, with respect to the total volume of the herbicide formulation.

[0032] As will be evident, the adhesion enhancer additive has the primary function of improving the adhesion of essential oils and vegetable oil to one or more target weeds. The adhesion enhancer additive, conveniently for the purposes of the present invention, is one or more paraffinic mineral oils, especially those used in agricultural applications. Examples of this type of adhesion enhancer additive are those marketed by LubLine® under the Harvestol® brand. Preferably, the herbicide formulations of the present invention include the adhesion enhancer additive in a proportion of 3.0% to 7.0% by volume, relative to the total volume of the herbicide formulation.Another key to achieving the superior performance and advantages of the herbicide formulations of the present invention is the presence of a light-protecting agent. This agent minimizes or prevents UV radiation from any light source, especially sunlight, from degrading the allelopathic compounds within the essential oils. In other words, the light-protecting agent helps minimize or prevent the degradation of the allelopathic compounds in the essential oils caused by UV radiation, allowing these compounds to remain structurally unchanged for a longer period after field application. This results in extended herbicidal action against one or more target weeds.Preferably, the light-protecting agent includes benzophenone (CAS number 119-61-9) in an amount that provides at least 200 mg of benzophenone per liter of herbicide formulation, preferably 200 mg to 300 mg of benzophenone per liter of herbicide formulation. It is also important that the light-protecting agent can be properly integrated and homogenized with the formulation using carriers or other facilitating substances, especially when it is a solid compound. For this reason, and conveniently, the light-protecting agent containing benzophenone is provided in the form of solutions, using one or more suitable solvents to facilitate its integration and homogenization with the other components.

[0033] Additionally, the non-selective herbicide formulations of the present invention may include additional or optional components that contribute to or help achieve one or more desired characteristics within the herbicide formulations. Examples, illustrative but not limiting, of such additional or optional components include other essential oils, suitable solvents, and / or additives known in the art, such as fragrances, viscosity modifiers, colorants, etc.

[0034] In a preferred embodiment, the non-selective herbicide formulation suitable for emulsification in water prior to use of the present invention includes cinnamon essential oil in a proportion of 30.0% by volume, with respect to the total volume of the herbicide formulation, rosemary oil in a proportion of 10.0% by volume, with respect to the total volume of the herbicide formulation, clove oil in a proportion of 15.0% by volume, with respect to the total volume of the herbicide formulation, geranium oil in a proportion of 5.0% by volume, with respect to the total volume of the herbicide formulation, coconut oil in a proportion of 30.0% by volume, with respect to the total volume of the herbicide formulation, polysorbate 80 in a proportion of 2.5% by volume, with respect to the total volume of the herbicide formulation, and paraffinic mineral oil in a proportion of 5.0% by volume, with respect to the total volume of the herbicide formulation, and a benzophenone solution (CAS number 119-61-9) in 96° GL (96% V / V) ethanol at 1.0% by weight / volume, said benzophenone solution being in a proportion of 2.5% by volume, with respect to the total volume of the herbicide formulation, to provide an amount of 250 mg of benzophenone per liter of herbicide formulation.

[0035] In at least one other object of the invention, a method for preparing the non-selective herbicide formulations suitable for emulsification in water prior to use of the present invention is generally carried out by adding the components of the herbicide formulations described above into a container of suitable capacity and mixing said components at a predetermined mixing speed for a predetermined mixing time. The predetermined mixing speed and mixing time are those at which integration and homogenization of the components of the herbicide formulation are achieved.

[0036] Conveniently, the method for preparing the herbicide formulations of the present invention is carried out by adding to a container of suitable capacity, in any order, the essential oils, mixing the essential oils, adding the vegetable oil with a lauric acid content of at least 30% by weight and mixing, adding the light-protecting agent, the emulsifying additive, and one or more paraffinic oils, and mixing them together.Preferably, the mixing speed and mixing time of the essential oils ranges from 200 rpm to 400 rpm and from 1 minute to 10 minutes, respectively; the mixing speed and mixing time of the vegetable oil ranges from 400 rpm to 800 rpm and from 5 minutes to 15 minutes, respectively; and the mixing speed and mixing time of the light protectant, emulsifying additive, and one or more paraffinic oils ranges from 800 rpm to 1400 rpm and from 20 minutes to 30 minutes.

[0037] For the preparation of the non-selective herbicide formulations of the present invention, as mentioned above, the essential oils are obtained through specific extraction processes. In this case, these processes include alcoholic or hydroalcoholic extraction and low-pressure distillation of cinnamon oil, supercritical fluid extraction with alcoholic cosolvents of rosemary essential oil, alcoholic or hydroalcoholic extraction and low-pressure distillation of clove essential oil, and alcoholic or hydroalcoholic extraction and low-pressure distillation of geranium essential oil. These specific extraction methods yield essential oils with herbicidal activity that, when combined, contribute to providing a superior non-selective herbicidal effect.

[0038] Another object of the invention relates to a herbicide composition in the form of an aqueous emulsion ready for application to one or more target weeds. In accordance with NOM-032-SAG / FITO-2014 (biological effectiveness ≥50%), the herbicide compositions in the form of an aqueous emulsion exhibit a herbicidal effect on weeds at a concentration of at least 2.0% of the non-selective herbicide formulation of the present invention from the first application. Preferably, these herbicide compositions include an amount of herbicide formulation corresponding to a concentration of 2.5% to 3.5% by volume, with respect to the total volume of the herbicide composition.

[0039] Furthermore, herbicidal compositions in the form of an aqueous emulsion can be prepared by providing a predetermined volume of water, adding a sufficient quantity of a non-selective herbicidal formulation of the present invention to achieve a herbicidal effect, that is, that the herbicidal formulations correspond to at least 2% by volume of the herbicidal compositions, and stirring the mixture of the predetermined volume of water and the herbicidal formulation until homogenized. Preferably, the quantity of herbicidal formulation corresponds to a concentration of 2.5% to 3.5% by volume with respect to the total volume of the herbicidal composition.

[0040] According to another object of the invention, it also relates to methods for the non-selective control of weeds by applying the herbicidal compositions in the form of an aqueous emulsion of the present invention to one or more target weeds. For application, any conventional technique known in the art may be used, for example, direct spraying.

[0041] With respect to the target weeds, as previously mentioned, these can be broadleaf (dicotyledons) or narrowleaf (monocotyledons). Examples, illustrative but not limiting, of broadleaf weeds susceptible to control by herbicide compositions including the non-selective herbicide formulation of the present invention are amaranth (Amaranthus hybridus L.), purslane (Portulaca oleracea), giant palm (Tithonia tubaeformis (Jacq.) Cass.), Bidens sp., field mugwort (Partheniuria hysterophorus L.), and morning glory (Iponoea purpurea L.). Likewise, illustrative but not limiting examples of narrow-leaf weeds that can be controlled by herbicide compositions that include the non-selective herbicide formulation of the present invention are guinea grass (Panicum maximum Jacq.) , the fox-tail or plumerillo (Setaria geniculata (Poiret) Kerguélen) , the small hedgehog or Honduran hedgehog (Ixophorus unisetus (K. Preesl) Schltdl) , the pinto hedgehog, striped or wild hedgehog (Echinochloa, mozonum) (Cenchrus echinatus L. ) and sunset bermuda or bramilla (Cynodon dactylon L. Pers . ) .

[0042] Likewise, any interval or range indicated throughout this document refers both to the set of extreme values ​​(lower and upper, inclusive) and to each value, separately, within the same range or interval, each such value being incorporated in the same way as if it were cited herein and both the extreme values ​​and the separate values ​​being constituents of any internal interval formed by them, within the larger interval where they are contained. For example, if an interval indicates values ​​from 25 to 30, it will mean that the values ​​26, 27, 28, and 29 are also being cited, as well as one or more of the internal intervals formed from the totality of values ​​present in the interval, that is, 25 to 26, 25 to 27, 25 to 28, 25 to 29, 26 to 27, 26 to 28, 26 to 29, 26 to 30, 27 to 28, 27 to 29, 27 to 30, 28 to 29, 28 to 30 and 29 to 30.

[0043] The following are some examples, which are intended to show only some modalities of the invention, and should not be understood as limiting its scope.

[0044] EXAMPLE 1. Obtaining essential oils

[0045] 1. 1 Cinnamon essential oil

[0046] In a 2000 L agitated tank, 250 kg of dried Cinnamomum verum bark were placed and macerated with 750 L of an ethanol:water extraction solution in a 25:75 volume ratio for 7 days, with gentle agitation (50-100 rpm) for 5 minutes every 24 hours. The pulp was separated from the macerate by vacuum filtration, yielding a liquid that was then distilled under reduced pressure (P± = 430 mbar, Pf = 100 mbar; T = 4°C, 50°C) to separate and recover the solvent used to extract the cinnamon essential oil. A yield of 12% was obtained (30 kg of essential oil with a relative density of 1.022 g / ml at room temperature).

[0047] The same extraction activities were carried out now for 40 kg of Cinnamomum cassia bark, obtaining a yield of 11.5% (4.6 kg of essential oil with a relative density of 1.028 g / ml at room temperature). 1. 2 Rosemary essential oil

[0048] Starting with 400 kg of dried stems and leaves of Salvia rosmarinas, an essential oil extraction was carried out using conventional equipment with supercritical fluid extraction, using supercritical CO2 as the solvent and ethanol (96°) as a co-solvent, at a pressure of 0.95 bar and 30°C. This yielded a cake of bagasse and essential oil, with a 2.3% yield (9.2 g of essential oil with a relative density of 0.913 g / ml at room temperature). This essential oil was stored in a sealed, opaque container of suitable capacity at room temperature and in the dark.

[0049] 1. 3 Clove essential oil

[0050] 150 kg of fresh leaves and flowers (buds) of Syzygium aromaticum are dried in a forced-air oven at 50°C to constant weight. The resulting dried plant material is macerated in a 1000 L tank with agitation, and macerated with 350 L of a methanol:ethanol extraction solution in a 25:75 volume ratio for 7 days, applying gentle agitation (50-100 rpm) for 5 minutes every 24 hours. The pulp is separated from the macerate by vacuum filtration, obtaining a liquid that is subjected to reduced-pressure distillation (P± = 430 mbar, Pf = 100 mbar; T = 4°C, 50°C) for the separation and recovery of the solvent used to extract the clove essential oil. A yield of 9.7% is obtained (14.55 kg of essential oil with a density of 1.052 g / ml at room temperature).

[0051] 1. 4 Geranium essential oil

[0052] 50 kg of fresh leaves, stems, and flowers of Pelargonium hortorum are dried in a forced-air oven at 50 °C to constant weight. The resulting dried plant material is macerated in a 1000 L tank with agitation, and macerated with 200 L of a methanol:water extraction solution in a 50:50 volume ratio for 7 days, applying gentle agitation (50–100 rpm) for 5 minutes every 24 hours. The pulp is separated from the macerate by vacuum filtration, obtaining a liquid that is subjected to reduced-pressure distillation (P± = 530 mbar, Pf = 75 mbar; T = 4 °C, 45 °C) for the separation and recovery of the solvent used to extract the geranium essential oil. A yield of 10.2% is obtained (5.1 kg of essential oil with a relative density of 0.880 g / ml).

[0053] The same extraction procedures were then performed on 10 kg of Pelargonium graveolens, yielding 10% (1 kg of essential oil with a relative density of 0.885 g / ml). This essential oil was stored in a sealed, opaque container of suitable capacity at room temperature and in darkness.

[0054] All the essential oils obtained are stored in appropriate opaque containers at room temperature (25°C) and kept in the dark. EXAMPLE 2. Herbicide Formulations

[0055] 2.1 Benzophenone solution.

[0056] 5.0 L of a 1% w / v benzophenone solution in 96° ethanol was prepared by dissolving approximately 50.50 grams of benzophenone (purity >99%, CAS number 119-61-9) in 2 L of 96° GL ethanol inside a 5.0 L volumetric flask and adding 96° GL ethanol to complete the volumetric flask.

[0057] 2.2 Preparation of herbicide formulations.

[0058] In a mixer with a propeller-type agitator, 10 L of each of the herbicide formulations of the invention and comparative formulations (CF), shown in Table 1, were prepared. For this purpose, the required amount of the essential oils obtained from Example 1 was added, and the mixture was stirred at 300 rpm for 5 minutes. The required amount of the vegetable oil(s) (conventional coconut oil and palm kernel oil) was then added, and the mixture was stirred at 600 rpm for 10 minutes. The required amounts of the previously prepared benzophenone solution, emulsifying additive(s) (Tween 20 and Tween 80), and adhesion-enhancing additive (Harvestol®) were added, and the mixture was stirred at 1100 rpm for 25 minutes. The comparative formulations (CF) were prepared without benzophenone (CFA) or by changing the proportion of essential oils (CFB, CFG). A 96° GL ethanol solvent has been used to complete the prepared herbicide formulations, where required.

[0059] Table 1. Herbicide formulations

[0060]

[0061] The formulations were stored at room temperature and in darkness until use.

[0062] EXAMPLE 3. Weed control in commercially valuable crops

[0063] 3.1 Red tomato (Solanum lycopersicum L.) variety Tisey

[0064] Experimental design. Aqueous compositions were prepared from the herbicide formulations of the invention and their respective comparative herbicide formulations in Table 1 (8 herbicide formulations in total), according to the method described, in concentrations: 2.0%, 2.5%, 3.0% and 3.5% by volume, for a total of 32 treatments including herbicide formulations and a blank treatment (0.0% herbicide formulation), resulting in a total of 33 treatments.

[0065] In an open-air plot of land in the municipality of Totolapan, Morelos, Mexico, without trees or other shading objects, a randomized complete block design was used, with 4 replicates per treatment, for a total of 132 experimental units. Each experimental unit had a usable area of ​​approximately 33.6 m². 2 (3 rows approximately 1.60 m wide x approximately 7.0 m long, with red tomato plants planted in said rows at a distance of 0.5 m from each other), so the total area of ​​each treatment is approximately 134.4 m 2 and the total surface area of ​​the arrangement is approximately 4,435.2 m² 2Within the usable area of ​​each experimental unit, only the central furrow was considered, and 0.5 meters were removed from each end of the experimental unit to avoid overlap between treatments across the width and length of the central furrow, respectively, so the usable treatment area is approximately 9.6 m² 2 (approximately 1.60 m wide x approximately 6.0 m long) .

[0066] The tests were conducted over 8 days. At the beginning (day 0), a quantitative assessment (biomass per square meter) was performed both at the start (pre-assessment) by randomly sampling a 0.5 m x 0.5 m quadrant, in duplicate, and at the end of the treatments (day 8) within the usable area, cutting the weeds at ground level and evaluating the fresh weight of aboveground biomass. A qualitative assessment was also carried out, identifying the weed species regularly found in the usable areas of the treatments, and visually determining the percentage of weed control by species and overall with respect to the control treatment in six samplings (day 1, day 2, day 3, day 5, day 6, and day 8), based on an EWRS (European Weed Research Society) scale applicable to the experiment, which can be seen in Table 2.Finally, the phytotoxicity of the treatments was evaluated in all experimental units, to identify negative symptoms on red tomato plants in the vegetative development phase, for example, round brown spots, rot, etc., in comparison with the white treatment B, based on the EWRS scale in Table 2, in six samplings (day 1, day 2, day 3, day 5, day 6 and day 8).

[0067] Table 2. EWRS Scale

[0068]

[0069] The aqueous herbicides were applied using SWISSMEX® brand manual sprayers with a nominal capacity of 15 L and a double-fan nozzle at a constant pressure of 2 bar. Each treatment area received a volume of 2.7 ± 0.1 L of aqueous herbicide (day 0 and day 2). The same volume (water) was used for the corresponding control area. The average temperature was 26.6°C, with an average relative humidity of 71.3%, an average rainfall of 5.6 mm (light rain on days 2, 5, 6, and 7), and an average solar radiation of 295.6 W / m². 2 , measures with conventional procedures and instruments.

[0070] In the biomass pre-assessment, the following initial weed biomass (BM) data, in grams per square meter, were collected for all treatments, including the control treatment (B), by weighing the weed biomass on a conventional digital scale and assigning it to the sampling areas (0.5 m x 0.5 m) shown in Table 3. The weeds were found in the early post-emergence stage (weeds up to 10 cm in size). Table 3. Initial weed biomass (pre-assessment)

[0071]

[0072] In the final biomass assessment (day 8), the live biomass in the control treatments increased to 176.50 ± 20.0 g, while in the treatments with comparative compositions it decreased to 13.25 ± 3.0 g. In the treatments with the compositions of the invention, the live biomass was practically zero. Regarding symptoms of phytotoxicity to the crop, no damage was observed from any of the treatments.

[0073] The weeds identified in the samples were Amaranthus hybridus L., Portulaca oleracea, Tithonia tubaeformis (Jacq.) Cass, Bidens sp., Panicum maximum Jacq., Setaria geniculata (Poiret) Kerguélen, Ixophorus unisetus (K. Preesl) Schltdl, and Echinochloa colonum. The corresponding qualitative evaluation of the treatments (2.0%, 2.5%, 3.0%, and 3.5%) was carried out for each of these weeds, as shown in Tables 4 to 11. Table 4. Aqueous herbicide compositions on Amaranthus hybridus L.

[0074]

[0075] In the results of Table 4, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Amaranthus hybridus L. At concentrations of 2.0% and above, the compositions of the invention achieved control greater than 50% from the first application, noted from the first evaluation, and reaching control of at least 87.5% at the lowest concentration (2.0%) after the second application, noted from the third evaluation, and control greater than 93.0% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor control, according to the EWRS scale. Table 5. Aqueous herbicide compositions on Portulaca oleracea.

[0076]

[0077] The results in Table 5 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Portulaca oleracea. At concentrations of 2.0% and above, the compositions of the invention achieved greater than 50% control from the first application, as noted in the first evaluation, and reached greater than 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the fourth evaluation. At concentrations of 2.5% and above, control exceeded 93.0% after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 6. Aqueous herbicide compositions on Tithonia tubaeformis (Jacq.).

[0078] Cass

[0079]

[0080] The results in Table 6 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Tithonia tubaeformis (Jacq.) Cass. At concentrations of 2.0% and above, the compositions of the invention achieved over 50% control from the first application, as noted in the first evaluation, and reached over 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, the compositions achieved at least 99.0% control after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 7. Aqueous herbicide compositions on Bidens s.

[0081]

[0082] In the results of Table 7, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Bidens sp. At concentrations of 2.0% and above, the compositions of the invention achieved control of more than 50% from the first application, noted from the first evaluation, and reaching control of at least 87.5% at the lowest concentration (2.0%) after the second application, noted from the third evaluation, and greater control of 96.5% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor and very poor control, according to the EWRS scale. Table 8. Aqueous herbicide compositions on Panicum maximum Jacq.

[0083]

[0084] The results in Table 8 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Panicum maximum Jacq. At concentrations of 2.0% and above, the compositions of the invention achieved greater than 50% control from the first application, as noted in the first evaluation, and reached greater than 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, control exceeded 96.5% after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor and very poor control, according to the EWRS scale. Table 9. Aqueous herbicide compositions on Setaria geniculata (Poiret).

[0085] Kerguélen.

[0086]

[0087] The results in Table 9 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Setaria geniculata (Poiret) Kerguélen. At concentrations of 2.0% and above, the compositions of the invention achieved greater than 50% control from the first application, as noted in the first evaluation, and reached greater than 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, control exceeded 93.0% after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor and very poor control, according to the EWRS scale. Table 10. Aqueous herbicide compositions on Ixophorus unisetus (K. Preesl) Schltdl.

[0088]

[0089] The results in Table 10 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Ixophorus unisetus (K. Preesl) Schltdl. At concentrations of 2.0% and above, the compositions of the invention achieved over 50% control from the first application, as noted in the first evaluation, and reached over 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, the compositions achieved at least 93.0% control after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor and very poor control, according to the EWRS scale. Table 11. Aqueous herbicide compositions on Echinochloa colonum.

[0090]

[0091] The results in Table 11 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Echinochloa colonum. At concentrations of 2.0% and above, the compositions of the invention achieved over 50% control from the first application, as noted in the first evaluation, and reached over 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, the compositions achieved at least 96.5% control after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations failed to achieve a minimum control of 50% in the first application at the tested concentrations, as noted in the first evaluation, reaching a final level of poor control, according to the EWRS scale. It is clear that the compositions prepared from a concentration of 2.0% by volume of the herbicide formulations with respect to the total volume of said compositions have a much superior performance from the first application compared to those compositions prepared with the comparative formulations and, of course, compared to the control treatment, in economically important crops, such as red tomatoes.This superior performance is attributed to the types of essential oils used, their proportion within the herbicide formulations of the present invention, and the presence of a protectant containing benzophenone in an amount effective in providing these essential oils with protection against solar UV radiation, typical of field conditions. It is further noted that compositions prepared from comparative formulations containing the benzophenone protectant within the claimed range exhibit superior performance (CBN, CFG), to varying degrees, compared to those lacking the protectant (CFA). This demonstrates the usefulness of this compound in improving the performance of herbicide formulations containing essential oils by protecting them from solar UV radiation in the field.Furthermore, since no evidence of phytotoxicity was found in the red tomato crop, the aqueous herbicide compositions prepared from the herbicide formulations of the present invention are safe for crops at least at the concentrations tested.

[0092] 3.2 Maize (Zea Mays L.) native variety (criolla-ancho).

[0093] Experimental design. Aqueous compositions were prepared from the herbicide formulations of the invention and their respective comparative herbicide formulations shown in Table 1 (8 herbicide formulations in total), according to the method described, in concentrations of: 2.0%, 2.5%, 3.0% and 3.5% by volume, for a total of 32 treatments including herbicide formulations and a blank treatment (0.0% herbicide formulation), resulting in a total of 33 treatments.

[0094] In an open-air plot of land in the municipality of Tepalcingo, Morelos, Mexico, without trees or other shading objects, a randomized complete block design was used, with 4 replicates per treatment, for a total of 132 experimental units. Each experimental unit had a usable area of ​​approximately 28.0 m². 2 (5 rows approximately 0.80 m wide x approximately 7.0 m long, with corn plants planted in said rows at a distance of 0.4 m from each other), so the total area of ​​each treatment is approximately 112.0 m 2 and the total surface area of ​​the arrangement is approximately 3,696.0 m 2Within the usable area of ​​each experimental unit, only the 3 central furrows of said experimental unit were taken, and 0.5 meters were removed from each end of the experimental unit to avoid overlap between treatments across the width and length of the central furrow, respectively, so the usable treatment area is approximately 14.4 m 2 (3 furrows approximately 0.8 m wide x approximately 6.0 m long) .

[0095] The tests were conducted over 8 days. At the beginning (day 0), a quantitative assessment (biomass per square meter) was performed both at the start (pre-assessment) by randomly sampling a 0.5 m x 0.5 m quadrant, in duplicate, and at the end of the treatments (day 8) within the usable area, cutting the weeds at ground level and evaluating the fresh weight of the aboveground biomass of the weeds. A qualitative assessment was also carried out, identifying the weed species regularly found in the usable areas of the treatments, and visually determining the percentage of weed control by species and overall with respect to the control treatment in six samplings (day 1, day 2, day 3, day 5, day 6, and day 8), based on the EWRS (European Weed Research Society) scale, which can be seen in Table 2 (corresponding to the previous experiment with the red tomato crop).Finally, the phytotoxicity of the treatments was evaluated in all experimental units, to identify negative symptoms on red tomato plants in the V2 phase, i.e., 2 true leaves unfolded, for example, round brown spots, rot, etc., in comparison with the white treatment B, based on the EWRS scale in Table 12, in six samplings (day 1, day 2, day 3, day 5, day 6 and day 8).

[0096] The aqueous herbicides were applied using SWISSMEX® brand manual sprayers with a nominal capacity of 15 L and a double-fan nozzle at a constant pressure of 2 bar. Each treatment area received a volume of 2.25 ± 0.05 L of aqueous herbicide (day 0 and day 2). The same volume (water) was used for the corresponding control area. The average temperature was 25.3°C, with an average relative humidity of 72.9%, 0.0 mm of average precipitation (no rain), and an average solar radiation of 304.4 W / m². 2 , measures with conventional procedures and instruments.

[0097] In the biomass pre-assessment, the following initial weed biomass data (BM), in grams, per square meter were collected for all treatments, including the white treatment (B), by weighing the weed biomass on a conventional digital scale and assigning it to the sampling areas (0.5 m x 0.5 m), shown in Table 12. The weeds were found in the early post-emergence phase (weeds with sizes up to 10 cm).

[0098] Table 12. Initial weed biomass (pre-assessment)

[0099]

[0100] In the final biomass evaluation (day 8), the live fresh biomass in the control treatments increased to 143.50 ± 15.0 g, while in the treatments with comparative compositions it decreased to 10.15 ± 2.0 g. In the treatments with the compositions of the invention, the live fresh biomass was practically zero. Regarding symptoms of phytotoxicity to the crop, no evidence of damage caused by the control treatment, the comparative compositions, or the herbicide compositions of the present invention at the tested concentrations was detected.

[0101] Los arvenses identificados en los muéstreos fueron Amaranthus hybrídus L. , Bidens sp. , Parthenium hysterophorus L. , Tithonia tubaeformis ( Jacq. ) Cass, Ipomoea purpurea L. , Cenchrus echinatus L. , Ixophorus unisetus (K. Preesl) Schltdl y Cynodon dactylon L. Pers . Se realizaron la evaluación cualitativa correspondiente de los tratamientos (2.0%, 2.5%, 3.0% y 3.5%) , para cada uno de dichos arvenses dentro de las Tablas 13 a 20.Tabla 13. Composiciones herbicidas acuosas sobre Amaranthus hybrídus L.

[0102]

[0103] In the results of Table 13, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Amaranthus hybridus L. At concentrations of 2.0% and above, the compositions of the invention obtained control greater than 50% from the first application, noted from the first evaluation, and reaching control greater than 87.5% at the lowest concentration (2.0%) after the second application, noted from the fourth evaluation, and control greater than 93.0% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 14. Aqueous herbicide compositions on Bidens sp.

[0104]

[0105] In the results of Table 14, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Bidens sp. At concentrations of 2.0% and above, the compositions of the invention achieved control greater than 50% from the first application, noted from the first evaluation, and reaching control greater than 87.5% at the lowest concentration (2.0%) after the second application, noted from the fourth evaluation, and control greater than 93.0% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 15. Aqueous herbicide compositions on Parthenium hysterophorus L.

[0106]

[0107] In the results of Table 15, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Parthenium hysterophorus L. At concentrations of 2.0% and above, the compositions of the invention achieved control greater than 50% from the first application, noted from the first evaluation, and reaching control greater than 87.5% at the lowest concentration (2.0%) after the second application, noted from the fourth evaluation, and control greater than 93.0% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of control from very poor to regular, the latter at the highest concentrations (3.0% and 3.5%), according to the EWRS scale. Table 16. Aqueous herbicide compositions on Tithonia tubaeformis (Jacq.) Cass.

[0108]

[0109] The results in Table 16 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Tithonia tubaeformis (Jacq.) Cass. At concentrations of 2.0% and above, the compositions of the invention achieved greater than 50% control from the first application, as noted in the first evaluation, and reached greater than 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the fourth evaluation. At concentrations of 2.5% and above, control exceeded 93.0% after the second application, resulting in control within the acceptable limits of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 17. Aqueous herbicide compositions on Ipomoea purpurea L.

[0110]

[0111] In the results of Table 17, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Ipomoea purpurea L. At concentrations of 2.0% and above, the compositions of the invention achieved control greater than 50% from the first application, noted from the first evaluation, and reaching control greater than 87.5% at the lowest concentration (2.0%) after the second application, noted from the fifth evaluation, and control greater than 93.0% at concentrations of 2.5% and above, after the second application, resulting in control within the acceptable limit of the EWRS scale.Conversely, all compositions prepared from comparative formulations did not achieve a minimum control of 50% in the first application at the tested concentrations, noted in the first evaluation, reaching a final level of poor or very poor control, according to the EWRS scale. Table 18. Aqueous herbicide compositions on Cenchrus echínatus L.

[0112]

[0113] In the results of Table 18, very significant differences are observed between the control treatment (B), without control at any point in the experiment according to the EWRS scale, with respect to the compositions of the invention at different concentrations on Cenchrus echinatus L. At concentrations of 2.0% and above, the compositions of the invention obtained control greater than 50% from the first application, noted from the first evaluation, and reaching control greater than 87.5% at the lowest concentration (2.0%) after the second application, noted from the third evaluation, and control greater than 99.0% at concentrations of 2.5% and above from the second application, also noted from the third evaluation, resulting in control within the acceptable limit of the EWRS scale.Although the compositions prepared from comparative formulations achieved a minimum control of 50% in the first application at a concentration of 2.5%, the final level of control obtained with them was at most regular according to the EWRS scale. Table 19. Aqueous herbicide compositions on Ixophorus unisetus (K. Presl) Schltdl.

[0114]

[0115] The results in Table 19 show highly significant differences between the control treatment (B), without control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Ixophorus unisetus (K. Presl) Schltdl. At concentrations of 2.0% and above, the compositions of the invention achieved greater than 50% control from the first application, as noted in the first evaluation, and reached greater than 87.5% control at the lowest concentration (2.0%) after the second application, as noted in the third evaluation. At concentrations of 2.5% and above, control exceeded 99.0% from the second application, also as noted in the third evaluation, resulting in control within the acceptable limits of the EWRS scale.Although the compositions prepared from comparative formulations achieved a minimum control of 50% in the first application at a concentration of 3.0%, the final level of control obtained with them was at most regular, according to the EWRS scale. Table 20. Aqueous herbicide compositions on Cynodon dactylon L. Pers.

[0116]

[0117] The results in Table 20 show highly significant differences between the control treatment (B), with no control at any point in the experiment according to the EWRS scale, and the compositions of the invention at different concentrations on Cynodon dactylon L. Pers. At concentrations of 2.0% and above, the compositions of the invention achieved over 50% control from the first application, as noted in the first evaluation, and reached over 87.5% control at the lowest concentration (2.0%), as noted in the second evaluation. At concentrations of 2.5% and above, after the second application, the compositions achieved at least 99.0% control, resulting in control within the acceptable limits of the EWRS scale. The compositions prepared from comparative formulations, while achieving a minimum control of 50% in the first application at a concentration of 2.0%, did not achieve the same level of control.5%, the final level of control obtained with them was at most regular, according to the EWRS scale. From the experiment with corn, similar conclusions and considerations are obtained to those obtained with the experiment of the red tomato, that is, that the compositions prepared from a concentration of 2.0% by volume of the herbicide formulations with respect to the total by volume of said compositions have a much superior performance from the first application with respect to those compositions prepared with the comparative formulations and white treatment, as well as the superior performance effect of the comparative formulations that contain benzophenone protectant agent with respect to those that lack it, which enable the use of said protectant agent (benzophenone) to improve the performance of herbicide compositions that include essential oils, and the safety of the herbicide formulations of the invention within aqueous compositions at least the concentrations tested for the non-selective control of weeds present in lands with crops of commercial interest.

[0118] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will be apparent to those skilled in the art. The invention is described in detail with reference to some particular embodiments, but it should be understood that various other modifications may be made and still be within the spirit and scope of the invention. It should be understood, therefore, that the appended claims are intended to cover all modifications and changes that fall within the true spirit of the invention.

Claims

CLAIMS 1. A non-selective herbicide formulation suitable for emulsification in water prior to use, comprising a) a plurality of essential oils, b) a vegetable oil having a lauric acid content of at least 30% by weight, c) an emulsifying additive, and d) an adherence-enhancing additive; characterized by a) The plurality of essential oils comprises: a) Cinnamon essential oil obtained from plants of the genus Cinnamomum, in a proportion of 27.0% by volume to 33% by volume, with respect to the total volume of the herbicide formulation; a2) rosemary essential oil obtained from the Salvia rosmarinas plant, in a proportion of 9.0% by volume to 11.0% by volume, with respect to the total volume of the herbicide formulation; a3) clove essential oil obtained from the Syzygium aromaticum plant, in a proportion of 13.0% by volume to 17% by volume, with respect to the total volume of the herbicide formulation; a4) geranium essential oil obtained from plants of the genus Pelargonium, in a proportion of 4.0% by volume to 6.0% by volume, with respect to the total volume of the herbicide formulation; b) Vegetable oil with a lauric acid content of at least 30% by weight is selected from coconut oil, palm kernel oil and mixtures thereof, in a proportion of 27.0% by volume to 33.0% by volume, with respect to the total volume of the herbicide formulation; c) the emulsifying additive is a non-ionic surfactant with an HLB of 8 to 16 that is an ethoxylated sorbitan derivative esterified with fatty acids; d) the adhesion-enhancing additive is one or more paraffinic mineral oils; and The herbicide formulation also includes: e) a light-protecting agent including benzophenone in a sufficient amount to provide at least 200 mg of benzophenone per liter of the herbicide formulation, preferably between 200 mg and 300 mg of benzophenone per liter of the herbicide formulation; f) optionally, a solvent.

2. The herbicide formulation according to claim 1, characterized in that the cinnamon essential oil is selected from an essential oil obtained from the Cinnamomum verum plant and a mixture of cinnamon essential oils from plants of the genus Cinnamomum that includes an essential oil obtained from the Cinnamomum verum plant in a major proportion (> 50% by volume) within said mixture.

3. The herbicide formulation, according to claim 1, characterized in that the essential oil of cinnamon is obtained by alcoholic or hydroalcoholic extraction and low pressure distillation.

4. The herbicide formulation, according to claim 1, characterized in that the rosemary essential oil is obtained by supercritical fluid extraction and alcoholic cosolvents under pressure.

5. The herbicide formulation, according to claim 1, characterized in that the clove essential oil is obtained by alcoholic or hydroalcoholic extraction and low-pressure distillation.

6. The herbicide formulation according to claim 1, characterized in that the geranium essential oil is selected from an essential oil obtained from the Pelargonium hortorum plant, the Pelargonium graveolens plant, and mixtures thereof.

7. The herbicide formulation, according to claim 1, characterized in that the geranium essential oil is obtained by alcoholic or hydroalcoholic extraction and low-pressure distillation.

8. The herbicide formulation according to claim 1, characterized in that the vegetable oil with a lauric acid content of at least 30% by weight of the total vegetable oil is selected from coconut oil, palm kernel oil and mixtures thereof.

9. The herbicide formulation according to claim 8, characterized in that coconut oil is the only vegetable oil with a lauric acid content of at least 30% by weight of the total vegetable oil within the herbicide formulation, or coconut oil is the major component (>50% by volume) of mixtures of coconut oil and palm kernel oil.

10. The herbicide formulation according to claim 1, characterized in that the fatty acid esterified ethoxylated sorbitan derivative is selected from polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 65, polysorbate 80, and mixtures thereof, preferably the fatty acid esterified ethoxylated sorbitan derivative is polysorbate 80.

11. The herbicide formulation according to claim 1, characterized in that the emulsifying additive is present in a proportion of 1.0% by volume to 5.0% by volume, with respect to the total volume of the herbicide formulation.

12. The herbicide formulation, according to claim 1, characterized in that the adhesion enhancer additive is present in a proportion of 3.0% by volume to 7.0% by volume, with respect to the total volume of the herbicide formulation.

13. The herbicide formulation according to claim 1, characterized in that the light-protecting agent including benzophenone is in solution form.

14. The herbicide formulation, according to claim 1, characterized in that it comprises: a) cinnamon essential oil in a proportion of 30.0% by volume, with respect to the total volume of the herbicide formulation, a2) rosemary oil in a proportion of 10.0% by volume, with respect to the total volume of the herbicide formulation, a3) clove oil in a proportion of 15.0% by volume, with respect to the total volume of the herbicide formulation, a4) geranium oil in a proportion of 5.0% by volume, with respect to the total volume of the herbicide formulation, b) coconut oil in a proportion of 30.0% by volume, with respect to the total volume of the herbicide formulation, c) polysorbate 80 in a proportion of 2.5% by volume, with respect to the total volume of the herbicide formulation, d) paraffinic mineral oil in a proportion of 5.0% by volume, with respect to the total volume of the herbicide formulation, and e) a benzophenone solution in 96° GL ethanol at 1.0% wt / v, said benzophenone solution being in a proportion of 2.5% by volume, with respect to the total volume of the herbicide formulation, to provide an amount of 250 mg of benzophenone per liter of herbicide formulation.

15. Method for preparing the non-selective herbicide formulation of claims 1 to 14, characterized in that it comprises the steps of: a) Add and homogenize by mixing at a predetermined speed and for a predetermined time, in a container of suitable capacity, in any order, the essential oil of cinnamon, the essential oil of rosemary, the essential oil of clove and the essential oil of geranium; b) add and homogenize by mixing at a predetermined speed and for a predetermined time the vegetable oil with a lauric acid content of at least 30% by weight with the mixture from step b); and d) Add, in any order, and homogenize by mixing at a predetermined speed and time the light-protecting agent, the emulsifying additive, and the one or more paraffinic oils essential oil with the mixture from step c).

16. The method, according to claim 15, characterized in that in step a) the predetermined speed varies from 200 rpm to 400 rpm and the predetermined time is from 1 minute to 10 minutes.

17. The method according to claim 15, characterized in that in step b) the predetermined speed varies from 400 rpm to 800 rpm and the predetermined time is from 5 minutes to 15 minutes.

18. The method according to claim 15, characterized in that in step c) the predetermined speed varies from 800 rpm to 1400 rpm and the predetermined time is from 20 minutes to 30 minutes.

19. The method according to claim 15, characterized in that the cinnamon essential oil is obtained from an alcoholic or hydroalcoholic extraction and low-pressure distillation of plants of the genus Cinnamomum, preferably Cinnamomum verum; and / or the rosemary essential oil is obtained from a supercritical fluid extraction and alcoholic cosolvents of Salvia rosmarinas; and / or the clove essential oil is obtained from an alcoholic or hydroalcoholic extraction and low-pressure distillation of Syzygium aromaticum; and / or the geranium essential oil is obtained from an alcoholic or hydroalcoholic extraction and low-pressure distillation of plants of the genus Pelargonium, preferably Pelargonium graveolens, Pelargonium hortorum or mixtures thereof.

20. A herbicidal composition in the form of an aqueous emulsion ready for application, characterized in that it comprises the non-selective herbicidal formulation of claims 1 to 14 or the herbicidal formulation prepared by the method of claims 15 to 19, in an amount corresponding to at least 2% by volume, with respect to the total volume of the herbicidal composition, and water.

21. The herbicide composition according to claim 20, characterized in that the herbicide formulation is at a concentration of 2.5% by volume to 3.5% by volume, with respect to the total volume of the herbicide composition.

22. A method for preparing the herbicidal composition in the form of an aqueous emulsion of claim 20 or 21, characterized in that it comprises the steps of: a) provide a predetermined volume of water; b) adding a quantity of the non-selective herbicide formulation of claims 1 to 14 or the herbicide formulation prepared by the method of claims 15 to 19, in an amount corresponding to at least 2% by volume, with respect to the total volume of the herbicide composition to the predetermined volume of water of step a); and c) Stir the mixture obtained in step b) until homogenized.

23. The method of claim 22, characterized in that the amount of the herbicide formulation corresponds to a concentration of 2.5% by volume to 3.5% by volume, with respect to the total volume of the herbicide composition.

24. A method for the non-selective control or eradication of weeds, characterized in that it comprises applying to one or more weeds the herbicide composition in the form of an aqueous emulsion of claim 20 or 21, or the herbicide composition in the form of an aqueous emulsion prepared by the method of claim 22 or 23.

25. Herbicide formulation based on essential oils, wherein said formulation comprises benzophenone as a light-protecting agent.

26. Herbicide composition in the form of an aqueous emulsion ready for application, wherein said composition comprises benzophenone as a light-protecting agent.

27. Use of benzophenone as a light protectant in herbicide formulations based on essential oils.

28. Use of benzophenone as a light protectant in herbicidal compositions in the form of ready-to-use aqueous emulsions, including essential oils.

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