WO2019130045A1 - Biocide-carrier matrix for controlling crawling pests, method for preparing the biocide-carrier matrix and use of the biocide-carrier matrix - Google Patents

Abstract

The invention relates to a biocide-carrier matrix for controlling crawling pests, which comprises: at least one lipophilic antioxidant; at least one surfactant; at least one photoprotector; at least one weak acid; solid petroleum jelly; liquid petroleum jelly; and at least one active ingredient that exercises biocidal activity. The invention also relates to a method for preparing and using the biocide-carrier matrix.

Description

 A BEARING MATRIX OF BIOCIDE FOR THE CONTROL OF TREPADORAS PESTS, METHOD OF PREPARATION OF THE CARRIER MATRIX OF

 BIOCIDA AND USE OF THE BIOCIDA CARRIER MATRIX

SCOPE

 The present invention is developed in the general field of the industry of agricultural biocides and biocides of surfaces. More specifically in the treatments for the control of climbing pests in agricultural lands, with special emphasis on the control of the Burrito de la vid {Naupactus xanthographus) and other species of similar habits.

 In the main, the invention relates to a matrix composed of a solid vehicle and a liquid vehicle, a lipophilic antioxidant, a surfactant, a physical sunscreen, a weak acid and an active principle comprising a fat-soluble biocide, and its method of elaboration. The matrix improves the effectiveness and effectiveness of the biocide incorporated in the control of infestation by climbing pests, particularly by the species Naupactus xanthographus. In addition, it is safe for those who handle it, friendly to the environment and allows the biocide not to be affected by the real environmental conditions of the field, does not affect the trees and requires few refills and low maintenance per season.

STATE OF ART

 The conventional technologies of this field of application point to the use of chemical compounds with biocidal activity, some of the most used are pyrethroids, organophosphates, among others. These active compounds are usually applied directly, or through solutions / reconstitutions, or through devices for controlling creeping insects, such as bands or control barriers based on polybutene and insecticide paint barriers containing carriers based on compounds like: Vaseline, gelatin and / or some natural or synthetic compounds.

Therefore, biocides can not only be applied directly, but also through vehicles that provide certain improvements to their provision. This is shown in document JP 03-090003, referred to the obtaining of a paint, capable of providing safe exterminating effects in a minimum amount required and effective against slugs, which adds an ingredient of bait, paste, preservative, extender, attractant, water , etc., to the metaldehyde as active ingredient and the resulting mixture forming a formulation such as an ointment. Within the same type of technology for pest control is the patent application US2012038865 which discloses a paint composition containing an insecticide and piperonyl butoxide as a synergist, where the amount of deltamethrin is in the range of 25 mg to 50 mg per liter of paint used and the amount of piperonyl butoxide is in the range of 12.5 mg to 1350 mg per liter of paint used.

 Depending on the mode of application of the biocides, the devices on which the biocide is applied are the closest technologies. However, the technologies described above exhibit clear drawbacks. For example, biocides applied directly or indirectly on the target, which can compromise their effectiveness and safety due to environmental factors, and also disappear after rain or by direct application of water or irrigation and can not be applied directly on the trunk.

SOLUTION OF THE PROBLEM OF THE TECHNIQUE

 The problems in table grapes, pomegranates, citrus and other crops due to the presence of Burrito de la vid (Naupactus xanthographus) and Capachito of fruit trees (Asynonychus cervinus) have increased in recent years in Chile. The negative impact caused by curculionidae in host crops is summarized in two types:

 Descartes quarantine: the Burrito de la vid was the cause of 47,800 boxes rejected in table grapevine and 3,048 apples in the 2009/10 season. In oranges, the curculionids detected as eggs under the rosette were involved in 50% of the rejections of the 2010-201 season 1 (69,357 boxes).

Loss of production due to root damage: the curculionids (burrito, capachito and others) have a polyphagous food habit with action at the root level, causing decrease in yield and quality (size) in vines and fruit trees, proportional to the degree of infestation.

 In the case of burrito, it can generate up to 80% decrease in productivity / quality of the fruit. Estimates, establish that 40% of the planted area of table vines (20,000 hectares), 8% of the vineyards (10,000 hectares), 40% of citrus fruits (5,000 hectares) and 15% of pits (6,000 hectares) are infested Relevant Consequently, costs are generated for phytosanitary management in the field, more rigorous inspections in packing or losses of value for re-destination.

In Chile, the Agricultural and Livestock Service (SAG) is the one that authorizes biocides for the control of pests, such as Naupacthus xanthographus. In particular, biocides more used are those referred to as contact, which for this case the common mechanism of action is chemical.

 One of the active compounds with greater biocidal activity is Indoxacarb, a product that belongs to the chemical group of oxadiazines, which has an insecticidal activity by ingestion and by contact. Indoxacarb acts by blocking the sodium channels of nerve cells, which causes poor coordination of movements, paralysis and death of the insect 24-60 hours after application; This process is called bioactivation. Symptoms appear quickly and insects are seen to stop eating 2-8 hours after application.

 Another active ingredient used is azinphosmethyl, which belongs to the group of organophosphates, synthetic organic substances formed by a phosphorus atom attached to 4 oxygen atoms or in some substances to 3 oxygen and one of sulfur. One of the phosphorus-oxygen bonds is quite labile and the phosphorus released from this "free group" is associated with acetylcholinesterase inhibiting nerve transmission and causing death. Its main characteristics are its high toxicity, its low chemical stability and its zero accumulation in the tissues, a characteristic that places it at an advantage over organochlorines of low degradability and high bioaccumulation.

 One of the ways to apply the biocides is by means of bands spread on a plastic sheet on the trunks of trees and shrubs.

 However, their costs are high and are estimated at USD $ 450-600 / ha / year, which in any case are lower than the solution of foliar applications, however, the present invention arises as a challenge to reduce even those costs.

 The solution delivered by the present invention comprises a toxic matrix applied on a plastic sheet placed on the trunk, which prevents the climbing of climbing insects to the tree, causing mortality of the harmful insects and avoiding the damage caused by these pests. This matrix is used as a base to be mixed with a biocide (synthetic or organic) of low toxicity and low environmental impact, which at the same time reduces costs related to curculionid control.

Primarily the present invention focuses on solving the problem of climbing pest control and does so through a composition whose final shape corresponds to an ointment. In addition, the present invention incorporates assets whose pharmaceutical function is that of a biocide, which sees its effectiveness, effectiveness and safety improved. Finally, the present invention increases the application intervals, since through this route a biocide can be applied in fewer opportunities during a period of time. Likewise, it improves the efficacy of the biocide, since by being in an ointment-shaped matrix, it achieves that the active one adheres to the insect increasing its contact time and therefore the possibility of exercising an activity on the plague leading to its death. Regarding safety, there are improvements as there is less contact between the biocide and the foliage and / or bark of the plant species in which the biocide will be applied, since a plastic band is placed around the trunk and / or guardian on which the present invention is applied, in addition its application form reduces the exposure to the applicators. This last aspect is of relevance for this type of industry, since it does not require a level of knowledge for the application or the use of complex or sophisticated personal protection elements or machinery for the application of pesticides.

DESCRIPTION OF THE FIGURES

 With reference to the drawings, a series of efficacy results of different formulations of the biocidal carrier matrix against certain pests are presented. Figure 1 shows the results of the effect of 4 biocides in mixture with matrix on adult mortality of curculionidae under laboratory conditions. This shows the effect, at 24 and 48 hours, of the biocides acetate, metidation, indoxacarb, fosmet and a control without application.

 Figure 2 shows the effectiveness of the matrix, at 24, 48 and 72 hours, with different active ingredients, on adults of N. xanthographus under laboratory conditions. The biocides tested comprise profenofos, thiamethoxam, indoxacarb, methomyl, lambda cyhalothrin, fipronil, acetamiprid and a control.

 Figure 3 shows the effect, at 24 and 96 hours, of two formulations and a control control of adults of Capachito of fruit trees, Naupactus cervinus, under field conditions. In this it was observed that at both 24 and 96 hours, the prototype NF15 achieved results similar to the results of the Pasta 82.4 GS product, validating its use.

Figure 4 illustrates the effect of the prototype barrier NF 15 on the control of Burrito adults of the vine, Naupactus xanthographus, under field conditions applied in a grape orchard. Where, again the prototype NF15 achieved results similar to the results obtained by the product Pasta 82.4 GS, as in figure 3. DETAILED DESCRIPTION OF THE INVENTION

 The present invention comprises a biocidal carrier matrix, comprising: at least one lipophilic antioxidant, at least one photoresist, at least one weak acid that improves the stability of the active ingredients, at least one surfactant having the ability to solubilize the ingredients active ingredients, solid petrolatum, liquid petrolatum and at least one active substance that will exert the biocidal activity.

 The biocidal carrier matrix specifically comprises:

 a) between 1 and 3% of at least one lipophilic antioxidant;

 b) between 6 and 9% of at least one surfactant;

 c) between 0.2 and 0.7% of at least one photoresist;

 d) between 0.2 and 0.7% of at least one weak acid;

 e) between 50 and 70% solid vehicle;

 f) between 20 and 40% of liquid vehicle; Y

 g) between 2 and 5% of active principle.

 The biocidal carrier matrix comprises at least one lipophilic antioxidant which is selected from tocopheryl acetate, carotenes (lycopene, b-carotene, zeaxanthin, astaxanthin, canthaxanthin) and lutein; ubiquinol (coenzyme Q) or other varieties of vitamin E (a-tocopherol).

 Also, the biocidal carrier matrix comprises at least one surfactant which is selected from sorbitan oleate, sorbitan monostearate (Span 60 ®), glycerin monostearate or glycerin monooleate;

 In the same way, the biocidal carrier matrix comprises at least one photoresist that is selected from titanium oxide, titanium dioxide or zinc oxide.

 In addition, the biocidal carrier matrix comprises at least one weak acid which is selected from lactic acid, citric acid or acetic acid.

 Also, the biocidal carrier matrix comprises a solid carrier corresponding to solid petrolatum and a liquid vehicle corresponding to liquid petrolatum.

Finally, the biocidal carrier matrix comprises at least one active principle that is selected from lipid-soluble biocides such as neonicotinoids, oxadiazines and / or organophosphates; more specifically indoxacarb, phosphoalkynes, phosphoalkenes, oxophosphines, thioxophosphines, iminophosphines, diphosphenes, phosphines, alkylphosphonous dihalide, dialkylphosphine halide, dialkylphosphonite, trialkylphosphite, dioxophosphorans, alkylmethaphosphate, methyleneophosphorane, bis (methylene) phosphorane, phosphonium ion, phosphonic acid, phosphinic acid, phosphine oxide, alkyl phosphate, dialkyl phosphate, trialkyl phosphate, phosphorus, acephate, metidation, indoxacarb, fosmet, profenofos, thiamethoxam, methomyl, lambda cyhalothrin, acetamiprid, fipronil.

 Each of the components of the formulation has particular properties. The lipophilic antioxidant prevents the oxidation of the active principle; the surfactant has the ability to solubilize the active ingredient in the matrix; the physical sunscreen prevents the oxidation of the active product of UV radiation; the weak acid improves the stability of the active, bringing the matrix to a pH of 4.5; an excipient that acts as a base and finally the active principle who will exercise the biocidal activity on the plague.

 The present invention also relates to the preparation of the biocidal carrier matrix, which comprises:

 a) mixing in a container (A) the at least one lipophilic antioxidant, the at least one surfactant and the at least one active principle in a temperature range between 80 ° C and 100 ° C until obtaining a uniform, transparent paste without lumps

 b) mixing, in a container (B), the solid base or vehicle and the liquid base or vehicle in a temperature range between 80 ° C and 100 ° C.

 c) once the mixture of both containers (A) and (B) is obtained, the mixture of the container (B) is added to the container (A) slowly, constantly and with vigorous agitation, reaching a speed between 250 to 450 rpm.

 d) Adding the at least one solar photoresist to the mixture obtained in step (c) with constant agitation.

 e) Add the at least one weak acid to the homogenized mixture of step (d) until reaching a pH in the range of 4.0 to 5.0.

f) Shake applying a mechanical force to mix until the final solution reaches 40 ^o C and acquires the ointment form.

In a preferred embodiment, the matrix with the active is applied on a sheet of biodegradable polyethylene or plastic, since it is sought to avoid direct contact of the ointment / matrix with the bark and the eventual occurrence of phytotoxicity in the trunk, which could affect seriously to plants in a medium to long term. They are older precautions when it comes to citrus and other trees that have a bark particularly sensitive to external agents.

 In a preferred embodiment, the polyethylene or biodegradable plastic sheet has a dimension of 20 to 25 cm high by 30 to 40 cm wide. The size of the sheet depends on the type and thickness of the tree trunk on which it will be applied. These sheets are preferably arranged in the tree at a height from 20 cm to 120 cm counted from the ground.

 The ointment / matrix contains at least one biocide, so that the people who apply it must be provided with personal protection elements such as an application suit, gloves to apply biocides, protective goggles and a filter mask.

 Furthermore, the use of the combination ointment / matrix and polyethylene sheet does not require special soil or climatic conditions. But if it is required, the trees where such a combination is applied should be fruit trees that do not present an abundance of basal shoots or "suckers" as for example happens in European hazelnut and quince.

 The main objective of this invention is to provide an effective, efficient and safe solution for the application and action of liposoluble biocides in the control of the infestation by insect pests climbers, specifically Naupactus xanthographus. This solution is also friendly to the environment and allows the biocide not to be affected by the real environmental conditions of the field, does not affect the trees, has a low frequency of change and maintenance per season.

 The matrix, which will be an impediment and an appropriate container for the active substance, is easy to apply, which will not deactivate the incorporated biocide molecule, it will be of low human toxicity and with low environmental impact, and will impregnate the plague in its rise to the foliage (climbing insects).

 In another embodiment, the matrix may be placed directly on the trunk. This aspect of the design is crucial, since it allows to reduce costs associated with the plastic material, the labor for installation, the risks for the health of the workers and the difficulty of final disposal.

APPLICATION EXAMPLE

Example 1 The matrix was tested with a series of biocides that act by contact, as well as by ingestion. They were mostly of the organophosphate type as the case of acephate, metidation and phosmet. With these samples, laboratory bioassays were conducted to evaluate the effectiveness and mortality, and the objective of the formulation was to evaluate the effect of these 3 biocides in a mixture with matrix on adult mortality of Curculionidae under laboratory conditions.

 The composition of the matrix tested comprises 1.94% tocopheryl acetate, 55.16% solid petrolatum, 7.6% sorbitan oleate, 0.48% titanium oxide, 0.39% lactic acid and 31%. 1 1% liquid petrolatum per 100 g respectively.

 Different mixtures were prepared separately using different biocides, with the same matrix base. The matrix mixture plus the biocide was placed on a piece of aluminum foil. The burrito adults of the vine were exposed to the matrices with biocides and then placed in a plastic container with vine leaves or alfalfa as a feeding substrate. The evaluation was made from 24 hours post exposure.

 Each treatment consisted of 4 repetitions. Twenty adults were used per treatment. The evaluations were made up to 72 hours post exposure. Accumulated mortality was determined.

 The mortality of adult burrito of the vine exceeded 80% in the first 24 hours and was close to 100% at 72 hours (see Figure 1). Such percentages of mortality were similar among the different biocides, despite belonging to different groups where certain mechanisms of action differ. All this with respect to the witness, who, because he did not have a biocide, had a mortality rate of 0.

Example 2

 The matrix was tested with the following biocides: profenofos, thiamethoxam, indoxacarb, methomyl, lambda cyhalothrin, fipronil and acetamiprid. The test was performed under laboratory conditions and the plague in question was Naupactus xanthographus.

 The composition of the matrix tested comprises 2.00% tocopheryl acetate, 62.70% solid petrolatum, 4.00% sorbitan oleate, 0.50% titanium oxide, 0.32% sorbitan monostearate ( 60 ®) and 30.08% liquid petrolatum per 100 g respectively.

The mixture was made separately from each of the different biocides indicated initially, with the matrix. The mixture of the most biocidal matrix was placed on a piece of aluminum foil. The burrito adults of the vine were exposed to the matrices and then placed in a plastic container with vine leaves or alfalfa as a feed substrate.

 Each treatment consisted of 4 repetitions. Twenty adults were used per treatment. The evaluations were carried out from 24 hours to 72 hours post exposure. Accumulated mortality was determined.

 In the first 24 hours of application of the matrix on Naupactus xanthographus. It is observed that the mortality rates are varied, being the highest those of thiamethoxam, fipronil, methomyl and indoxacarb. This tendency was maintained at 48 hours and 72 hours, with the exception of thiamethoxam (see Figure 2).

Example 3

 The composition of the tested matrix comprises 2.00% tocopheryl acetate, 62.60% solid petrolatum, 4.00% sorbitan oleate, 0.50% titanium oxide, 0.40% lactic acid, 0, 5% glycerin monostearate and 29.60% liquid petrolatum per 100 g respectively.

 The matrix was applied with a brush on polyethylene sheet or biodegradable plastic previously placed around the trunk of the trees. For the evaluation of the adults a sheet was placed under the tree and / or plant and the branches or main arms are struck using a rubber mallet, the adult insects fall on the plastic and are counted. The trial consisted of 3 treatments, including a control without application and 4 repetitions per treatment.

 The graph of Figure 3 shows control results of the adults of Capachito of the fruit trees with the matrix of the present application containing as biocide indoxacarb (Prototype NF15), observing a decrease in the average abundance of adults with respect to the control and treatment standard (Prototype 82.4). The standard treatment corresponding to prototype 82.4 contains petrolatum as a matrix and azinphos-methyl as biocide.

Example 4

The composition of the tested matrix comprises 2.00% tocopheryl acetate, 62.30% solid petrolatum, 4.00% sorbitan oleate, 0.50% titanium oxide, 0.40% lactic acid, 0, 5% glycerin monostearate and 30.00% liquid petrolatum per 100 g respectively. The already formulated matrix, with the indoxacarb biocide (Prototype NF15.) Was applied in a grape orchard. The conditions in which it was applied were of field and the objective plague was on the control of adults of Burrito of the vine, Naupactus xanthographus. Up to 1 10 DDA there was no loss of consistency or runoff of the pulp in the polyethylene or in the vines (See Figure 4). This also shows the results of the control and commercial product Banda 82.4 GS; where the latter contains petrolatum as a matrix and azinphos-methyl as a biocide.

Claims

one . A biocidal carrier matrix for the control of climbing pests, CHARACTERIZED because it comprises: at least one lipophilic antioxidant, at least one surfactant, at least one photoprotector, at least one weak acid, solid petrolatum, liquid petrolatum and at least one active substance that will exert the biocidal activity.  2. The biocidal carrier matrix of claim 1, CHARACTERIZED because it specifically comprises:  a) between 1 and 3% of at least one lipophilic antioxidant;  b) between 6 and 9% of at least one surfactant;  c) between 0.2 and 0.7% of at least one photoresist;  d) between 0.2 and 0.7% of at least one weak acid;  e) between 50 and 70% of solid petrolatum;  f) between 20 and 40% liquid petrolatum; Y  g) between 2 and 5% of at least one active ingredient.  3. The biocidal carrier matrix of claims 1 and 2, CHARACTERIZED in that the at least one lipophilic antioxidant is selected from tocopheryl acetate, carotenes, ubiquinol and vitamin E.  4. The biocidal carrier matrix of claims 3, CHARACTERIZED because the carotenes are selected from lycopene, b-carotene, zeaxanthin, astaxanthin, canthaxanthin and lutein.  5. The biocidal carrier matrix of claims 1 and 2, CHARACTERIZED in that the at least one surfactant is selected from sorbitan oleate, sorbitan monostearate, glycerin monostearate or glycerin monooleate.  6. The biocidal carrier matrix of claims 1 and 2, CHARACTERIZED in that the at least one photoresist is selected from titanium oxide, titanium dioxide or zinc oxide. 7. The biocidal carrier matrix of claims 1 and 2, CHARACTERIZED in that the at least one weak acid is selected from lactic acid, citric acid or acetic acid. 8. The biocidal carrier matrix of claims 1 and 2, CHARACTERIZED in that the at least one active ingredient is selected from lipid-soluble biocides, such as neonicotinoids, oxadiazines, organophosphates; more specifically  9. Method of preparing the biocidal carrier matrix of claim 1, CHARACTERIZED because it comprises:  a) mixing in a container (A) the at least one lipophilic antioxidant, the at least one surfactant and the at least one active principle in a temperature range between 80 ° C and 100 ° C until obtaining a uniform, transparent paste without lumps;  b) mixing, in another container (B), the solid vehicle and the liquid vehicle in a temperature range between 80 ° C and 100 ° C;  c) adding the mixture of the container (B) over the container (A) slowly, constantly and with vigorous agitation, until reaching a speed between 250 to 450 rpm;  d) adding the at least one sun photoprotector to the mixture obtained in step (c) while maintaining constant agitation;  e) adding the at least one weak acid to the homogenized mixture of step (d) until reaching a pH in the range of 4.0 to 5.0; Y f) shake applying a mechanical force to mix until the final solution reaches 40 ^o C and acquires the ointment form.  10. Use of the biocidal carrier matrix according to the preceding claims, CHARACTERIZED because it comprises applying said matrix on a sheet of biodegradable polyethylene or plastic, wherein said sheets are arranged on the tree at a height from 20 cm up to 120 cm counted from the ground.  1. Use of the biocidal carrier matrix according to claim 10, CHARACTERIZED because the polyethylene or biodegradable plastic sheet has a dimension between 10 and 50 cm high by 10 to 50 cm wide.  12. Use of the biocidal carrier matrix according to claims 10 and 11, characterized in that the polyethylene or biodegradable plastic sheet has a dimension between 20 and 25 cm high by 30 and 40 cm wide.