ES2875536A1 - Coated fabrics for use in agriculture and livestock (Machine-translation by Google Translate, not legally binding) - Google Patents

Abstract

The present invention is related to fabrics coated with pesticidal substances, preferably insecticide and as an insect repellent, its manufacture and its use in the agricultural and livestock sectors. Likewise, in their use as repellants and in the prevention and treatment of agricultural crops against insects, as well as the kits and methods for said treatments. (Machine-translation by Google Translate, not legally binding)

Description

Coated fabrics for use in agriculture and livestock

TECHNICAL FIELD

The present invention is related to fabrics coated with pesticidal substances, preferably insecticide and / or as an insect repellent, their manufacture and their use in the agricultural and livestock sectors. Likewise, in their use as insect repellants and in the prevention and treatment of agricultural crops against insects, as well as the kits and methods related to said treatments.

BACKGROUND OF THE INVENTION

The use of insecticide-coated mosquito nets in humans to prevent arthropod bites is widely known. The use of mosquito nets is particularly important in countries where arthropods transmit disease (eg malaria).

The use of coated fabrics has also spread, in a more moderate way to cover vegetables or fruits, as a way to protect them against arthropods, such as insects, myriapods or arachnids. This allows reducing the contamination that occurs with the massive use of pesticides and insecticides of the parts of the plant that are eaten later.

One of the main factors in the manufacture and marketing of nets or fabrics used to prevent mosquito or other insect bites is to ensure their effectiveness while minimizing the loss of active ingredient in a fabric treated or coated with said active. For example, a mosquito net treated with insecticide is a very relevant factor in preventing the contagion and transmission of diseases.

Some of the materials or fabrics most used in the manufacture of mosquito nets coated with insecticides such as deltamethrin, are polyester, polyethylene or polypropylene, however, these have the disadvantage of their low durability. In the case of polyethylenes or polypropylenes, they are also rougher and not very pleasant to the touch. As described in WO-2008/004711, WO-2008/032844 or EP2557916, said disclosures attempt to improve the adhesion of deltamethrin by making use of methods of melt extrusion of materials such as polyethylenes or polypropylenes.

Later, patent CN105200800A, described fabrics coated with microcapsules of peppermint oil in a concentration between 0.025% w / p to 0.33% w / w, at least one ethylene vinyl acetate polymer fixative and an anti-wrinkle resin of the type glyoxal and imidazole. The use of these fabrics was destined to the manufacture of curtains, bedding, mosquito nets or carpets

The use of these coated fabrics has spread mainly to mosquito nets, curtains and clothing. However, it has spread more modestly to the field of agriculture.

Taking into account the importance of the agricultural and livestock sector in the southern regions of Europe and the need to increase and make production profitable, while reducing the transmission of diseases, it is necessary to develop methods and tissues that are adequate to protect and / or treat crops and as an insect repellent on crops and livestock.

Consequently, the present invention provides solutions to the problems mentioned above, through the use of fabrics coated with compounds with pesticidal activity which are effective in the prevention or treatment of diseases caused by insects in agriculture, as well as to act as a repellent of insects in livestock animals. These new coated fabrics can maintain this activity over time, even if they are outdoors, thus avoiding having to remove and change them frequently both in animals and in extensive plantations. Furthermore, these coated fabrics have the advantage that they can be obtained through industrially viable methods and with good yields.

BRIEF DESCRIPTION OF THE INVENTION

The first aspect of the invention is related to a fabric with pesticidal activity, characterized in that the fabric is coated with:

- at least one fixing agent selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof;

- at least defoamer;

- and at least one compound with pesticidal activity, selected from the list consisting of the compound of formula I,

and the compound of formula III

The tissues of the first aspect are useful for use in plant crops and livestock as pesticides. In the context of this invention, "cultivation of plants" is understood to be agricultural and ornamental plants, unless otherwise specifically indicated. In the context of this invention, a pesticide is understood to be any substance intended to prevent, destroy, attract, repel or combat any pest, including unwanted species of plants or animals, during the production, storage, transport, distribution and processing of food. , agricultural products or animal feed, or that can be administered to animals to combat ectoparasites. The term pesticides includes insecticides, miticides, and insect repellants.

Therefore, a compound with pesticidal activity is intended to prevent, kill, arrest the development, attract, repel or combat any live arthropod infestation or prevent their action. In the context of the present invention in is understood by insecticidal activity of a substance to prevent, destroy, attract, repel or combat any pest of insects, during the production, storage, transport, distribution and processing of food, agricultural products, animals or animal feed, or that can be administered to or in contact with animals or plants against insects. In the context of the invention, pesticides can be insecticides and insect repellants. An insecticide is defined as a chemical compound used to kill insects, prevent, destroy, attract, repel or combat any of these pests for use in both animal and plant species. In the context of the present invention, the compound with pesticidal activity refers to the compound I, or the compound II or the compound III or mixtures thereof.

In particular, the fabric of the invention is effective and provides good insecticidal activity, as well as insect repellent when it comes into contact with or in close proximity to silver crops. Preferably against the green peach aphid (Myzus persicae), the vinegar fly of the closed wings (Drosophila suzukii) and the weevil of the cerelaes (Sitophilus zeamais). It also has a good effectiveness as a repellent for insects, such as mosquitoes, when placed near or on any part of the body of livestock animals.

In addition, the fabric of the first aspect has the advantage that it can be subjected to multiple washes while maintaining its pesticidal activity and keeping the pesticidal compound adhered to the fabric over time, even when it is outdoors, thus avoiding having to remove them and change them frequently both in animals and in extensive plantations.

Other advantages of the fabric of the first aspect is that it is soft so that it does not irritate or damage the skin of the animal and at the same time it is flexible enough to be able to adapt to the different parts of the animal's body where it can be placed, to for its effect as a pesticide to take place.

Also, the coated fabric of the first aspect also has the advantage that can be obtained through industrially viable methods and with good yields.

The second aspect of the invention is related to a process to obtain the fabric of the first aspect that comprises at least the at least the steps of:

a) Prepare an aqueous composition for coating fabrics comprising:

- at least one fixing agent selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof;

- at least one compound with pesticidal activity, selected from the list consisting of the compound of formula I, the compound of formula II, the compound of formula III, or mixtures thereof;

- at least one defoamer;

- a pH regulator,

where the pH of the aqueous composition is between 5-6;

b) impregnating a fabric with the composition obtained in the previous stage, where the process is carried out in a temperature range between 10 to 30 ° C;

c) subjecting the fabric obtained in the previous step to a process to eliminate the aqueous solvent;

temperature range between 20 to 80 ° C;

e) subjecting the fabric obtained in the previous stage to a curing process in a temperature range between 120 to 150 ° C.

The process of this second aspect is obtained through industrially viable methods and provides good yields, while facilitating good adhesion and fixation of the compound with pesticidal activity to the fabric fibers once the process is completed. The process facilitates the adhesion of the compound with pesticidal activity that is maintained over time ensuring the effectiveness of the fabric as an insecticide and insect repellent even when it has remained indoors or outdoors after months of application. The process also allows the tissue obtained to be soft so that it does not irritate or damage the skin of the animal and at the same time is flexible enough to be able to adapt to the different parts of the animal's body where it can be located, so that its effect as pesticide to take place.

The third aspect of the invention is related to the use of the tissue of the first aspect and the tissue obtained through the process of the second aspect for the prevention and / or treatment of diseases caused by insects against livestock animals and / or against crops. of plants.

The fourth aspect of the invention is related to the use of the fabric of the first aspect and the fabric obtained through the process of the second aspect as an insect repellent in livestock animals and / or against plant crops. Preferably, to repel the bites of insects and / or arachnids, such as mosquitoes, ticks, flies, lice, spiders, bed bugs and / or termites.

The fifth aspect of the invention is related to a kit comprising the following elements:

- (i) a piece of coated fabric of the first aspect or the fabric obtained through the process of the second aspect

- (ii) a box or container containing the piece of tissue of element (i).

- (iii) a brochure with instructions for use of the product.

The fifth aspect kit is suitable and effective for use in the prevention and / or treatment of diseases caused by insects in plant crops, both agricultural and ornamental, as well as as a repellent against insects in plant crops and against livestock animals. .

The sixth aspect of the invention is related to a method for the prevention and / or treatment of diseases caused by insects in plant crops or as an insect repellent in plant crops that comprises at least the steps:

- Provide the fifth aspect kit;

- Placing the piece of coated tissue of the first aspect or the tissue that comprises the kit of the fifth aspect, in proximity or in contact with the plant culture that suffers a disease that can be prevented or treated with compound I, compound II, compound III or with a mixture of both, with at least one effective dose of said compounds, comprised in the tissue or in the kit of the fifth aspect.

Preferably, in plant crops they are agricultural and / or ornamental plant crops, by pests of agricultural crops or ornamental plants

The seventh aspect of the invention is related to the kit of the fifth aspect for use in the prevention of diseases caused by insects in animals and as an insect repellent in livestock animals. Preferably, the insects are selected from a list consisting of, mosquitoes, ticks, flies, spiders, lice, bed bugs, and termites. More preferably as a mosquito repellent.

The eighth aspect of the invention is related to a method to prevent diseases caused by insects in livestock animals and / or repel insect bites in livestock animals that comprises at least the steps:

- Provide the fifth aspect kit;

- Placing the piece of coated tissue that comprises the kit of the fifth aspect, in proximity or in contact with the animal, where said tissue comprises an effective dose of compounds II and / or III.

DETAILED DESCRIPTION OF THE INVENTION

The first aspect of the invention is related to a fabric with pesticidal activity, characterized in that the fabric is coated with:

- at least one fixing agent comprising at least one substance selected from the list consisting of cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof;

- at least defoamer;

It consists of the compound of formula I, the compound of formula II and the compound of formula III.

In the context of this invention, substances or compounds with pesticidal activity are understood to have insecticidal and / or insect repellent activity. These can be pyrethroid compounds, such as deltamethrin or permethrin. Deltamethrin is a synthetic pyrethroid with broad spectrum insecticidal and acaricidal activity, referred to in the context of this invention as a compound of formula I (compound I). It is also known by its chemical name [(1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropane carboxylate of (S) -alpha-cyano-3-phenoxybenzyl. Compound I has the following structure

Compound of formula I

In the context of the present invention, an insect repellent is a substance applied to the skin, clothing, fabrics or other surfaces that prevents insects and arthropods in general from climbing or climbing on these surfaces. In the context of this invention, an insect repellent, such as lice or mosquitoes, would be IR3535, also known by its chemical formula Ethyl 3- [acetyl (butyl) amino] propanoate and is referred to as a compound of formula II (compound II) .

Compound of formula II

Permethrin is a synthetic chemical that belongs to the family of compounds called pyrethroids and is used as an insecticide and miticide, as well as a repellent for insects and lice. It is also known by its chemical name (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate and is referred to as the compound and formula III (compound III) that has the structure indicated next.

Compound of formula III

In a preferred embodiment of the first aspect of the invention, compound II is in the tissue in the form of nanoparticles. Said nanoparticles have a mean particle size, D50, in the range from 50 nm to 1 nm.

The term "Dx" in the context of the invention means that x% of the particles of the substance or composition (based on volume) have a diameter equal to or less than a value specified by Dx. Therefore, a D50 of 50 nm means that 50% of the particles, measured by volume, have a diameter equal to or less than 50 nm. In the same way that D50 is used as a measure to determine particle size, D90 can also be used for this purpose. Therefore, D90, means that 90% of the particle population (based on volume) has a diameter equal to or less than the established D90 value. Particle size can be measured through various conventional methods including electron microscopy using a scanning electron microscope (SEM).

In a preferred embodiment of the first aspect of the invention, the fabric further comprises silicon particles, which improve the dispersion and incorporation of the compounds with pesticidal activity into the fibers of the fabric. It also helps to improve the binding of the compound with pesticidal activity to the fabric during the manufacturing process, ensuring this effect after 1 month of application. More preferably, the fabric comprises silicon particles and the compound of formula II.

In a particular embodiment, compound I and compound III are present in the fabric in an amount ranging from 200 to 1700 mg / m2 of fabric. Preferably, between a amount in a range between 400 to 800 mg / m2 of tissue. In another particular embodiment, compound II is present in the fabric in an amount ranging from 200 to 2700 mg / m2 of fabric. Preferably, enter an amount in a range between 400 to 2000 mg / m2 of fabric. More preferably, between an amount in a range between 500 to 1600 mg / m2 of fabric.

In a particular embodiment of the first and second aspects, the compound with pesticidal activity that is used to coat the fabric can also comprise mixtures of the compound of formula I, the compound of formula II and the compound of formula III. When the compound with pesticidal activity comprises mixtures of several compounds, the compound of formula II is present relative to the compound of formula I or formula III, in a weight ratio within a range of 1: 1 to 1:20. Said fabric has very good insecticidal and insect repellent activity at the same time. In this way, the process makes it possible to prepare both a fabric with a good insecticidal activity for the prevention and / or treatment of diseases caused by insects and at the same time with a good activity as an insect repellent.

The fabric according to the first and second aspects of the invention is a fabric comprising threads of natural, artificial and / or synthetic fibers. Natural ones come from plants or animals, and can be selected from the list that consists of cotton, wool, linen, silk and blends of these. Man-made fibers are manufactured from natural raw materials and can be selected from the list consisting of rayon, viscose, lyocell, and mixtures of these. Synthetic fibers are produced by chemical and natural processes and can be selected from the list consisting of polyester, polyamides such as nylon, acetate, and mixtures of these. Fabrics with a mixture of fibers are also manufactured to achieve the qualities of the different materials in a garment. Preferably, the fabric is selected from cotton, polyesters, and polyamides. The fabric may be of the knitted type or of the flat or openwork type. The untreated fabric can have a weight of between 120 to 500 mg / m2. Preferably, the grammage of the untreated fabric is between 200 to 350 mg / m2.

In a preferred embodiment of the first and second aspects, the fixative comprises a silane compound selected from the list consisting of 3-glycidyloxypropyl trimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, 3-aminopropyltriethoxysilane, organimetho-reactive aminopropyltriethoxysilane, organophylanoxysilane fluoro-allylfunctional oligosilane, 3-glycidyloxy propyltriethoxysilane, 3-trimethoxysilyl-propyl methacrylate, 3-trimethoxysilyl-propyl acrylate, 3 dimethoxysilane, 3-Glycidyloxy-propyl-methyl-diethoxysilane, or mixtures thereof. Thus preferably, the binder is a silane compound selected from the list consisting of 3-glycidyloxypropyl trimethoxysilane, octyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-methyl-diethoxysilane, organo-functional reactive oligosilane in water, oligosilane fluoroallyl 3-diethoxymethyl-silyl propan-1-amino, 3-Glycidyloxy-propyl-methyldiethoxysilane, 3-glycidyloxypropyl-methyl-dimethoxysilane, and mixtures thereof. Even more preferably, the fabric comprises a silane compound, as described in the preceding paragraphs, and the compound of formula II. Said combination provides very good properties to the fabric by improving the adhesion of the compound of formula II, a good release of compound II and ensuring the efficacy of compound II with pesticidal activity over time, even under harsh environmental conditions while providing a good durability of the fabric after washing and outdoors. It also provides and therefore good efficacy. Preferably the fabric exhibits good pesticidal efficacy after 1 month, more preferably after 3 months, even more preferably after 6 months.

In a preferred embodiment of the first and second aspects, if the fixative comprises silane it is present with a mean particle size D (50) between 90-500 nm, more preferably between 120-250 nm. These preferred ranges provide good adhesion of Compound II to fabric fibers, providing good efficacy of Compound II over time, even under harsh environmental conditions. At the same time, it provides a good durability of the fabric to washing and outdoors.

In a preferred embodiment of the first and second aspects, the fixing agent comprises a crosslinked polyether polyurethane, a polysaccharide or a water soluble or dispersible silane compound, in an amount of at least 40% by weight, more preferably in an amount of at least 35% by weight, which allows a better dispersion and application of the fixative and the pesticide on the fabric while providing a good adhesion of the substance with pesticidal activity on the fibers of the fabric.

In a preferred embodiment of the first and second aspects, the fixing agent comprises at least one crosslinked polyurethane polymer of aliphatic and / or aromatic polyethers. More preferably, the aliphatic and / or aromatic polyether crosslinked polyurethane polymer is amphoteric and provides a pH in water of between 4.5-6 at room temperature. Ambient temperature can vary in a range between 15-25 ° C. Even more preferably, said polyether cross-linked polyurethane polymer is dispersed in the fabric in a droplet size less than 100 nm, which improves the penetration of the fixative and durability and resistance of the fabric to washing and weathering, ensuring the effectiveness of the compound with pesticidal activity over time. Preferably, the fabric exhibits good pesticidal efficacy, after 1 month, more preferably after 3 months, even more preferably, after 6 months.

In a preferred embodiment of the first of the second aspect of the invention, when the fixative is a polysaccharide polymer, the polysaccharide polymer is hydrophobic and has a glass transition temperature (Tg) in the range from -10 to 40 ° C.

In a preferred embodiment of the process of the first and second aspects of the invention, the fixing agent does not comprise formaldehyde, organotin compounds, or co-solvents selected from the list consisting of dimethylformamide, methyl ethyl ketone, n-methylpyrrolidone, and n-ethylpyrrolidone. The absence of these substances provides a more sustainable and cleaner process at an environmental level. In a preferred embodiment of the first aspect of the invention, the fixing agent does not comprise polyvinylpyrrolidone (PVP).

In a preferred embodiment of the first and second aspects of the invention, the compound with pesticidal activity is in a ratio by weight with reference to the fixative in a range between 5: 1 to 1: 3. Preferably the ratio is in a range between 4: 1 to 1: 2. More preferably, in a range between 3: 1 to 1: 1.

The fabric of the first aspect of the invention comprises at least one defoamer. The first and second aspect defoamer destroys foaming. The defoamers of the present invention are defoamers comprising silicone. In a particular embodiment of the first and second aspects, the antifoams contain silicone oils that act as antifoam liquids. The defoamers of the present invention are chemically inert; they do not negatively affect the action of surfactants and it prevents the foams that may be generated by the process of moving the bath from becoming increasingly solid and more difficult to remove. In a preferred embodiment of the first and second aspects, the defoamer comprises silicone in a manner that prevents or reduces soiling of fabrics during the preparation process.

In a preferred embodiment, the fabric of the first aspect of the invention may comprise at least one softener. Preferably the softener of the first and second aspect contains silicone, which gives the fabric a good touch, little manufacturing.

In a particular embodiment, the softener of the first and second aspects can be polydimethylsiloxane, fluid emulsions of aminosilicones or silicone elastomers, such as high molecular weight polysiloxanes with terminal functional reactive groups (-SiH or -SiOH) that with suitable catalysts produce their corresponding crosslinks to to form a network structure with terminal functional reactive groups of silanol (SiOH).

The fabric of the first aspect of the invention may comprise at least one antibacterial. The antibacterial of the first and second aspects when present helps to improve the odor of the fabric and to prevent or slow the microbial growth of the coated fabric of the first aspect. In a preferred embodiment, the antibacterial comprises zeolites.

The second aspect of the invention is related to a process to obtain the fabric of the first aspect, said process comprises at least the steps of:

a) Prepare an aqueous composition for coating fabrics comprising:

- at least one fixing agent, selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof;

- at least one compound with pesticidal activity, selected from the list consisting of the compound of formula I, the compound of formula II, compound III or mixtures thereof;

- at least one defoamer;

- a pH regulator,

where the pH of the aqueous composition is between 5 to 6.5;

b) impregnating a fabric with the composition obtained in the previous stage, where the process is carried out in a temperature range between 10 to 40 ° C;

c) subjecting the fabric obtained in the previous step to a process to eliminate the aqueous solvent;

d) subjecting the fabric obtained in the previous stage to a drying process in a temperature range between 20 to 80 ° C;

e) subjecting the fabric obtained in the previous stage to a curing process in a temperature range between 120 to 150 ° C.

citric acid / citrate. Sufficient amount is added to obtain a pH of the aqueous composition of step a) between 5-6.5, preferably between 5-6. Preferably the pH regulator is a citric acid / citrate buffer.

It is important to take into account the humidity or the percentage of humidity that the fabric has before and after carrying out the process of the second aspect, to apply the necessary amount of the compound with pesticidal activity. So that if the fabric is too wet pesticidal substance concentration is increased so that the amount of pesticide applied per m ² of fabric. After the manufacturing process of the coated fabric is completed, the amount of pesticidal active compound remaining in the fabric is determined. To determine the amount of compound I or compound II comprised in the tissue, it is carried out by taking a tissue sample and analyzing it by means of analytical means such as chromatography, for example, HPLC (high-performance liquid chromatography).

In a preferred embodiment of the second aspect, the process where the process of impregnating the fabric of step b) is carried out by dipping, soaking or spraying said fabric in the composition of the previous step.

In a preferred embodiment of the second aspect process, the drying of step d) is carried out with hot air, which prevents the loss of less compound with pesticidal activity in its manufacture and ensures the effectiveness of the coated fabric.

In a preferred embodiment of the process of the second aspect, the aqueous composition comprises the compound of formula I and / or the compound of formula III and the fixing agent contains at least one cross-linked polyether polyurethane or a polysaccharide, or mixtures thereof.

In a preferred embodiment of the process of the second aspect, the aqueous composition of step a) comprises an antifoam comprising silicone. The silicone defoamer comprises all the characteristics already mentioned for the first aspect and provides the previously mentioned advantages in the first aspect.

In a preferred embodiment of the process of the second aspect, the aqueous composition of step a) optionally comprises an antibacterial, silicon particles and / or a softener. More preferably, the softener comprises silicone and / or the antibacterial. mentioned in the first aspect.

In a preferred embodiment of the process of the second aspect, the fabric is subjected to a pretreatment process before undergoing the coating process, that is, before step a), the pretreatment process comprises at least the following steps:

i) Incorporate to the untreated fabric at least one oil;

ii) incorporating into the fabric of the previous step at least one lubricant; and iii) removing the oil and lubricant used in steps a) and b) through a process in which the fabric is treated with softened water, caustic soda and a surfactant at a temperature ranging from 30 to 70 ° C.

This pretreatment process improves the coating process of the fabric pieces to be treated with the composition of step a) of the second aspect since it prevents the threads from splitting and reduces breakage. It also makes it easier for the machines that work the fabric to do so with the least possible resistance.

In a more preferred embodiment of the process of the second aspect, the pretreatment process prior to step a) further comprises the following steps:

iv) Once stage iii) is completed, a bleaching process is carried out treating the fabric with a composition that comprises:

water, caustic soda, chelating compounds and detergents at a temperature between 30 ° and 70 ° C;

v) a mixture of hydrogen peroxide, soda and a hydrogen peroxide stabilizer is added and said mixture is stirred for a period of between 20 and 60 minutes kept at a temperature between 75 ° and 90 ° C;

vi) the peroxide remaining in the tissue is denatured through the use of catalases followed by neutralization of the tissue through the use of buffers and / or acids until any excess soda is removed from the tissue;

vii) optionally, the fabric is dyed through the use of dyes or colorants; viii) the fabric obtained in stage f) or g) is subjected to a rinsing stage until the salts obtained in the previous stages are eliminated.

The use of chelating products has the advantage that it helps to eliminate a possible trace in the form of rust if metallic needles are used and they prevent burns in the threads of the fabric and consequently the presence of holes.

They are selected from the list consisting of sodium silicate, sodium orthophosphate and tripolyphosphate, borax and sodium acetate. Preferably the stabilizer is sodium silicate. The peroxide stabilizer prevents immediate decomposition due to the alkalinity of the water and oxygen bath. The temperature range of stage v) allows us to perform a chemical bleaching and remove the brown tones that the fibers of the fabric may have, keeping the temperature in a range between 75 ° to 90 ° of temperature.

In a more preferred embodiment of the process of the second aspect, the aqueous composition of step a) when compound with pesticidal activity is compound I or compound III, comprises at least the following components:

- compound I or compound III in a concentration range between 2 to 30 g / l;

- at least one fixing agent containing at least one polymer selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide, or mixtures thereof, in a concentration range between 0.5 to 10 g / l ; - at least one softener in a concentration range between 1 to 4 g / l;

- at least antifoam in a concentration range from 0.05 to 3 g / l; - at least antibacterial in a concentration range between 0.1 to 2% by weight with respect to the grams of fabric, measured in g / m2;

- a pH regulator in a concentration range between 0.1 to 5 g / l.

Therefore, if the antibacterial is in a concentration of 2%, and the fabric is 250 g / m2, 5 grams of antibacterial will be used.

In a more preferred embodiment of the second aspect, the compound of formula I is in a concentration range between 3-20 g / l, even more preferred between 4-12 g / l.

In a more preferred embodiment of the process of the second aspect, the aqueous composition of step a) when compound with pesticidal activity is compound II, comprises:

- the compound of formula II in a concentration range between 2-45 g / l;

- at least one fixing agent containing at least one silane in a concentration range between 0.4-25 g / l;

- at least one softener in a concentration range between 1-4 g / l;

- at least antifoam in a concentration range from 0.05 to 3 g / l; - at least antibacterial in a concentration range between 0.1-2% by weight with respect to the grams of fabric, measured in g / m2;

In a more preferred embodiment of the second aspect, the compound of formula II is in a concentration range between 3-30 g / l, even more preferred between 5-20 g / l.

The third aspect of the invention is related to the use of the fabric of the first aspect or the fabric obtained through the process of the second aspect in the present invention, the treatment and / or as a repellent against insects in plant crops. Preferably, the agricultural plant crops are selected from a list consisting of cereals, fruits and vegetables and / or the pest insects are selected from the list consisting of, Myzla, Drosophila suzukii and Sitophilus zeamais.

In a preferred embodiment of the third aspect, the fruits selected from the list consisting of strawberries, grapes, oranges, lemons, tangerines, blueberries and raspberries; the vegetables selected from the list consisting of pepper, eggplant, tomato, lettuce, zucchini and cucumbers and / or the crops are selected from agricultural crops, selected from the list consisting of rice, corn, wheat and rye or ornamental plant crops .

The fourth aspect of the invention is related to the use of the fabric of the first aspect or the fabric obtainable by the process of the second aspect in livestock animals to repel the bite of insects. Livestock animals includes cattle, cattle, cattle, pigs, goats, horses, birds and rabbits.

In a preferred embodiment, the insects are selected from the list consisting of, mosquitoes, ticks, flies, lice, bed bugs, and termites.

The fifth aspect of the invention is related to a kit comprising the following elements:

- (i) a piece of fabric covered according to fabric of the first aspect or fabric obtainable through the process of the second aspect;

- (ii) a box or container containing the piece of fabric of element (i);

- (iii) a brochure with instructions for use of the product for the treatment or prevention of diseases.

The box or package of this aspect may comprise a cardboard or plastic package or box.

prevention, treatment and / or as a repellent against insects in crops of agricultural or ornamental plants.

The seventh aspect of the invention is related to a method for the prevention and / or treatment of diseases caused by insects or as a repellent against insects, in crops that comprises at least the stages:

- Providing a piece of coated fabric of the first aspect or the piece of fabric of the kit of the fifth aspect;

- Place the piece of coated tissue that comprises the kit of the fifth aspect, in proximity or in contact with the agricultural crop that suffers a disease that can be prevented or treated with compound I, compound II, compound III or with a mixture of both, with at least an effective dose of said compounds, comprised in said kit.

In the context of the present invention, the term in contact is defined as that the tissue is directly in partial or total contact over its entire length with any part of the plant or animal.

In the context of the present invention, the term "proximity" is defined as that the tissue is at a very close distance to any part of the plant or animal, sufficient to be effective in treatment or as a repellent. For example, in the case of the animal, the fabric is in proximity if it is placed on a strap or ear tag or any similar element. In the case of a plant, the tissue is in proximity, if the tissue is hung from a support to which the plant is also attached or if it is placed around the plant partially or totally covering it.

Preferably the culture is an agricultural or ornamental plant culture and / or where the insect pests are selected from the list consisting of Myzla, Drosophila suzukii and Sitophilus zeamais.

The eighth aspect of the invention is related to the use of the fifth aspect for its use in the prevention of diseases caused by insects and / or as an insect repellent, in livestock animals.

The ninth aspect of the invention is related to a method to repel insect bites in livestock animals that comprises at least the steps:

- Provide the fifth aspect kit;

proximity or in contact with the animal, wherein said tissue comprises an effective dose of compounds II and / or III.

In a preferred embodiment of the ninth aspect, the piece of tissue is placed around the neck of the animal or a device attached to the ear of the animal, said device being adapted to comprise said tissue or on the leg of the animal. Even more preferred, the device can be an ear tag or an elastic strap. In general, livestock animals include cattle, cattle, cattle, pigs, goats, horses, birds and rabbits.

In a more preferred embodiment of the ninth aspect, the tissue can be left in contact with or in proximity to the animal for at least 3 months.

Example 1: Composition of a fabric coated with compound I

Table 1: tissue components from example 1

Example 2: Composition of a fabric coated with compound II

Table 2: tissue components of example 2.

Example 3: Preparation of the tissue of example 1

A cotton fabric with a grammage of 230 g / m2 on which the pre-treatment process of step a) has been carried out is obtained wet once it has been removed from the dyeing and / or bleaching machines. The tissue pieces were drained and dried. At the end of this stage coating the fabric with compound I, in order to adjust the amount of compound I to be added.

A composition (a) comprising the components and amounts described below in Table 3 was prepared.

Table 3: Components and amounts of the composition used to prepare the fabric process of the example!

Next, the fabric was immersed in a bath containing composition (a) for a time interval between 20 min and 2 hours at a temperature in a range between 10-30 ° C. Then the fabric obtained in the previous stage was subjected to a draining process in which rubber cylinders were used. Once the fabric has been drained, it is transferred to drying chambers where it is dried with hot air at a temperature between 20-70 ° C and subsequently the curing process is carried out at a temperature of 130 ° C. Finally, these pieces according to example 1, are rolled, packed and protected to be able to go to the cutting and making process.

It should be taken into account that the amount of compound I that is added in the composition is adjusted taking into account that during the process between 20-35% is not absorbed by the fibers of the fabric or evaporates during the drying and curing stage.

Example 4: Preparation of the tissue of example 2

A cotton fabric with a grammage of 240 g / m2 on which the pre-treatment process of step a) has been carried out is obtained wet once it has been removed from the dyeing and / or bleaching machines. The tissue pieces were drained and dried. At the end of this stage, it is advisable to know the percentage of humidity before carrying out the stage to cover the fabric with compound I, in order to adjust the amount of compound I to be added.

down in table 4.

Table 4 : Components and amounts of the composition used to prepare the fabric process of example 2.

Next, the fabric was immersed in a bath containing composition (a) for a time interval between 20 min and 2 hours at a temperature in the range between 20-40 ° C. Then the fabric obtained in the previous stage was subjected to a draining process in which rubber cylinders were used. Once the fabric has been drained, it is transferred to drying chambers where it is dried with hot air at a temperature between 20-80 ° C and subsequently the curing process is carried out at a temperature of 135 ° C. Finally, these pieces according to the composition of example 2 are rolled, packed and protected to be able to go to the cutting and making process.

Tissue efficacy tests

The pesticidal efficacy of the tissues was tested in mice (Swiss albino mouse species) against insects (Aedes aegypti mosquito species). The test measures the effectiveness of the treatment when the coated tissues of the invention are used against Aedes aegypti mosquitoes, in this case to protect mice against the bites of these insects. For this test I provide the kit of the invention comprising the tissue of example 2.

For this, the absence or presence of bites, landing and repellency are identified. The term sting refers to an insect penetrating the skin with parts of its mouth and ingesting blood.

The term landing refers to an insect that lands in the exposed area on the mouse, but does not probe or bite.

The term "repellency" refers to the absence of landing or probing of the insect on the skin of the mouse where the repellent has been applied or placed.

The effectiveness of the fabric as an insect repellent was measured by calculating the percent effectiveness of the fabric as an insect repellent. The Efficiency Percentage indicates the reduction the number of landings recorded in the control sample at the beginning of the repetition and calculated at the end of each trial.

% Efficiency = 100- Landing on the treated sample * 100

Landing on the control sample

Test conditions

Use was made of the fabric of example 2 that was incorporated in the kit of the fifth aspect. The tissue was placed in a 20,000 cm3 cubic cage with a sleeved opening to insert the subject's arm into the cage. The test chamber is made of net (walls and top) and white cloth (bottom).

The temperature was kept between 25 ° C and 27 ° C and the relative humidity between 60% and 80%. An artificial source of illumination was used. In each cage, there is a water source available.

Two time zones were tested: European time zone and Brazilian time zone.

Mosquito reset technique:

The larvae and pupae are reared in optimal conditions at 27 ° C, relative humidity 80 ° C at 10%, and a 16: 8 hour photoperiod (light: dark). Feeding the adults is done by providing a cotton pad soaked with a 10% sucrose solution. No blood meal is given before the test. Mosquitoes starve for 12 hours before the test. The test insects are used for a single test, and are incinerated after the test.

Number of mosquitoes tested: 100 per cage per repetition.

Repellency test

The test is carried out in a square repellent test chamber, with a mosquito net as walls and a mosquito net cover and underneath white cloth, under laboratory conditions. A mouse is kept in a cage with a dense net with its eyes protected. A tissue sample from Example 2 is wrapped around the mouse and placed into the test chamber. The time interval for each study is one hour (60 min). The number of mosquitoes landed on the target and on the material is recorded for one hour. The knockdown effect on insects is also observed and noted. The identical procedure is followed for various configurations.

Test results

In the European time zone - the tissue sample has shown very good repellent efficacy of 95.34% in the mouse and an excellent repellent effect of 100% efficacy in the sample compared to the control. In the Brazilian time zone the tissue sample has shown very good repellent efficacy of 91.02% in the mouse and an excellent repellent effect of 100% efficacy in the sample compared to the control.

Evaluation of the efficacy of the coated fabrics of the invention against insect pests.

In this laboratory test, the susceptibility of 2 species of pest insects (the green peach aphid, Myzus persicae and the vinegar fly of the spotted wings), in the coated fabrics of the invention, has been evaluated. In particular in the fabric of Example 1.

Test conditions.

4m2 of untreated fabric and 2 m2 of fabric treated according to the invention were used (example 1). Tissues were stored in sealed bags at room temperature until testing. 13x16 cm pieces were cut and each piece of fabric was taped to the base of a 22x16x7.5 cm transparent box with adhesive tape, leaving approximately half of the box base without fabric.

Inside each box, in the middle of the tissue piece, a pepper leaf with the petiole was placed in a water tube, 2-3 strawberries were also placed, depending on whether the insect to be evaluated was the aphid or the fly, respectively.

10 replications were made for each species and treatment. The pepper leaves had not been previously treated with any chemical insecticide. The strawberries came from organic cash crops. Subsequently, in the middle of each box (at the confluence between the part of the box where there was cloth and the one that did not exist), 15 aphids were released (for the samples with peppers), 5 female flies (for the samples with strawberries). ).

After 1h and 24h, the living and dead individuals were counted. In the case of the fly, these initially introduced individuals were removed from the box after 24 h, while the aphid was left in the same box for the duration of the experiment (72 h). The strawberries were incubated for 13 days in ventilated plastic cups.

Incubations were carried out in a climatic chamber at controlled temperature and humidity (25 ° C for strawberries and 28 ° C for rice; 70% RH). When the descendant adults emerged, the number of individuals obtained by repetition was counted. The number of dead and alive aphids, and the number of dead flies at the sampling times were compared by analysis of variance (ANOVA) followed by a test of comparison of means between treatments.

Results with the aphid M. persicae (pepper)

At the beginning of the experiment, 15 individuals were introduced per box.

The number of live aphids when the tissue of example 1 has been used is very small compared to the control, both after one hour after the start of the experiment and after 24 hours and after 72 hours, providing very good efficacy in prevention. of diseases caused by the aphid M. persica on the pepper plant.

Table 5. Number of live and dead aphids after 1h, 24h and 72h.

Results with the fly D. suzukii

At the beginning of the experiment, 5 individuals were introduced per box. The number of live aphids when the tissue of example 1 has been used is very small compared to the control, both after one hour after the start of the experiment and after 1h and after 24 hours, providing very good efficacy in prevention. of diseases caused by the fly D. Suzukii in both strawberries and blackberries. The same trials were performed with blackberries, providing the same good results as are seen with strawberries.

Table 6. Number of live and dead flies after 1 hour and 24 hours with strawberries.

Claims (54)

1. A fabric with pesticidal activity, characterized in that the fabric is coated with: - at least one fixing agent comprising at least one substance selected from the list consisting of cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof; - at least one compound with pesticidal activity, selected from the list consisting of the compound of formula I 23456

and the compound of formula III;

- and at least one defoamer. 2. The fabric according to the preceding claim, wherein the compound with pesticidal activity also comprises mixtures of the compound of formula I, the compound of formula II and the compound of formula III; The fabric according to the preceding claim, wherein the compound of formula II with respect to the compound of formula I or the compound of formula III, is present in a ratio by weight in a range between 1: 1 to 1:20. 4. The fabric according to any of claims 1-3, wherein compound II is in the form of nanoparticles. 5. The fabric according to any of the preceding claims, further comprising silicon particles. 6. The fabric according to any of the preceding claims, wherein the cross-linked polyurethane is a cross-linked polyurethane of aliphatic and / or aromatic polyethers. 7. The fabric according to the preceding claim, wherein the cross-linked polyurethane of aliphatic and / or aromatic polyethers is amphoteric and provides a pH in water of between 4.5-6 at room temperature. The fabric according to any one of the preceding claims, wherein the polyether cross-linked polyurethane polymer is dispersed in the fabric in a droplet size of less than 100 nm. The fabric according to any one of claims 1-5, wherein the fixative is a silane compound selected from the list consisting of 3-glycidyloxypropyl trimethoxysilane, octyltriethoxysilane, octyltrimethoxysilane, propyltriethoxysilane, propyltrimethoxysilane, 3-aminopropyltriethoxysilane, olimetho-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, olimethoxypropylanoxysilane, Organofunctional reagent in water fluoro-allylfunctional oligosilane, 3-glycidyloxy propyltriethoxysilane, 3-trimethoxysilyl-propyl methacrylate, 3-trimethoxysilyl-propyl acrylate, 3-aminopropyl-methyl-diethoxysilane, 3-diethoxymethyl-silyl propan-1-aminopropyl-3-aminopropyl-propan-1-aminopropyl -methyl-dimethoxysilane, 3-Glycidyloxy-propyl-methyl-diethoxysilane or mixtures thereof. The fabric according to the preceding claim, wherein the fixative is a silane compound selected from the list consisting of 3-glycidyloxypropyl trimethoxysilane, octyltriethoxysilane, 3-aminopropyl-triethoxysilane, 3-aminopropyl-methyl-diethoxysilane, organofunctional reactive silane oligomer in water, fluoroallyl functional reactive silane oligomer in water, organofunctional reactive in water, 3-diethoxymethyl-silyl propan-1-amino, 3-Glycidyloxy-propyl-methyl-diethoxysilane, 3-glycidyloxypropyl-methyldimethoxysilane, and mixtures thereof. The fabric according to any of claims 1-5, wherein the polysaccharide is a hydrophobic polysaccharide. 12. The fabric according to any of the preceding claims, wherein the fixative does not contain formaldehyde, organotin compounds, or co-solvents selected from the list consisting of dimethylformamide, methyl ethyl ketone, n-methylpyrrolidone and n-ethylpyrrolidone. The fabric according to any of the preceding claims comprising an amount of compound I or compound III in a range between 200 mg to 1700 mg per m2 of fabric. 14. The fabric according to any of the preceding claims comprising an amount of compound I or compound III in a range between 250 mg to 1200 mg per m2 of fabric. 15. The fabric according to any of the preceding claims comprising an amount of compound II in a range from 200 mg to 2700 mg per m2 of fabric. 16. The fabric according to any of the preceding claims comprising an amount of compound II in a range between 400 mg to 2000 mg per m2 of fabric. 17. The fabric according to any of the preceding claims, wherein the weight ratio of the compound with pesticidal activity with reference to the fixative is in a range between 5: 1 to 1: 3. 18. The fabric according to any of the preceding claims, wherein the weight ratio of the compound with pesticidal activity with reference to the fixative is in a range between 4: 1 to 1: 2. 19. The fabric according to any of the preceding claims, wherein the weight ratio of the compound with pesticidal activity with reference to the fixative is in a range between 3: 1 to 1: 1. 20. The fabric according to any of the preceding claims, wherein the fabric is a fabric comprising natural, artificial or synthetic fibers. 21. The fabric according to any of the preceding claims, wherein the defoamer essentially comprises silicone. 22. The fabric according to any of the preceding claims further comprising at least one softener. 23. The fabric according to any of the preceding claims, wherein the softener essentially comprises silicone. 24. The fabric according to any of the preceding claims, wherein it further comprises at least one antibacterial. 25. The fabric according to any of the preceding claims, wherein the antibacterial comprises zeolites. 26. A process for obtaining the fabric according to claims 1-25 comprising at least the steps of: a) Prepare an aqueous composition for coating fabrics comprising: - at least one fixing agent selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide, a silane or mixtures thereof; - at least one compound with pesticidal activity, selected from the list consisting of the compound of formula I, the compound of formula II and compound III; - at least one defoamer; - a pH regulator; where the pH of the aqueous composition is between 5 to 6.5; b) impregnating a fabric with the composition obtained in the previous stage, where the process is carried out in a temperature range between 10 to 40 ° C; c) subjecting the fabric obtained in the previous step to a process to eliminate the aqueous solvent; d) subjecting the fabric obtained in the previous stage to a drying process in a temperature range between 20 to 90 ° C; e) subjecting the fabric obtained in the previous stage to a curing process in a temperature range between 120 to 150 ° C. 27. The process according to the preceding claim wherein compound with pesticidal activity comprises mixtures of the compound of formula I, compound of formula II and the compound of formula III. 28. The process according to the preceding claim wherein the compound of formula II with respect to the compound of formula I or the compound of formula III, is present in a ratio by weight in a range between 1: 1 to 1:20. 29. The process according to any of claims 26-28 wherein the drying of step d) is carried out with hot air. 30. The process according to any of claims 26-29 wherein the process of impregnating the fabric of step b) is carried out by dipping, soaking or spraying said fabric with the composition of the previous step. 31. The process according to claim 26 wherein the cross-linked polyurethane is a cross-linked polyurethane of aliphatic and / or aromatic polyethers. 32. The process according to the preceding claim, wherein the fixative is added as an aqueous dispersion comprising at least one crosslinked polyether polyurethane dispersing at a droplet size of less than 100 nm. 33. The process according to any of claims 26-32, wherein the aqueous composition comprises an antibacterial, silicon particles and / or a softener. 34. The process according to any of claims 26-33, wherein the softener comprises silicone. 35. The process according to any of claims 26-34, wherein the antibacterial comprises zeolites. 36. The process according to any of claims 26-35 wherein the fabric is subjected to a pre-treatment process before step a) comprising the steps: i) Incorporate to the untreated fabric at least one oil; ii) Incorporate into the fabric of the previous stage at least one lubricant; and iii) Eliminate the oil and lubricant used in steps a) and b) by means of a process in which the fabric is treated with softened water, caustic soda and a surfactant at a temperature ranging from 30 to 70 ° C. 37. The process according to the preceding claim, further comprising the following steps: iv) Once stage iii) is completed, a bleaching process is carried out treating the fabric with a composition that comprises: water, caustic soda, chelating compounds and detergents at a temperature between 30 ° and 70 ° C; v) a mixture of hydrogen peroxide, soda and a hydrogen peroxide stabilizer is added followed by stirring said mixture for a period of time between 20 and 60 minutes, keeping the temperature between 75 ° and 90 ° C; vi) the peroxide remaining in the tissue is denatured through the use of catalases followed by neutralization of the tissue through the use of buffers and / or acids until any excess soda is removed from the tissue; vii) optionally, the fabric is dyed through the use of dyes or colorants; viii) and the fabric obtained in step f) or g) is subjected to a rinsing step until the salts obtained in the previous steps are removed. 38. The process according to any of claims 26-37 wherein the aqueous composition of step a) when compound with pesticidal activity is compound I or compound III, comprises: - compound I or compound III in a concentration range between 2 to 30 g / l; - at least one fixing agent comprising at least one polymer selected from the list consisting of a cross-linked polyether polyurethane, a polysaccharide or mixtures thereof; where the fixing agent is in a concentration range between 0.5 to 10 g / l; - at least one softener in a concentration range between 1 to 4 g / l; - at least antifoam in a concentration range from 0.05 to 3 g / l; - at least antibacterial in a concentration range between 0.1 to 2% by weight with respect to the grams of fabric, measured in g / m2; - a pH regulator in a concentration range between 0.1 to 5 g / l. 39. The process according to any of claims 26-37 where the aqueous composition of step a) when compound with pesticidal activity is compound II, comprises: - the compound of formula II in a concentration range between 2-45 g / l; - at least one fixing agent containing at least one silane, in a concentration range between 0.4-25 g / l; - at least one softener in a concentration range between 1-4 g / l; - at least antifoam in a concentration range from 0.05 to 3 g / l; - at least antibacterial in a concentration range between 0.1-2% by weight with respect to the grams of fabric, measured in g / m2; - a pH regulator in a concentration range between 0.1-5 g / l. 40. Use of the fabric according to any of claims 1-25 or obtainable by the process according to claims 26-39 in the prevention and / or treatment of diseases caused by insects or arachnids in agricultural crops. 41. The use of the coated fabric according to the preceding claim wherein the agricultural crops are selected from a list consisting of, ornamental plants, cereals, fruits and vegetables and / or the insects of agricultural pests are selected from the list consisting of, Myzla , Drosophila suzukii and Sitophilus zeamais. 42. The use of the coated fabric according to the preceding claim, wherein the fruits are selected from the list consisting of strawberries, grapes, oranges, lemons, blueberries and raspberries and / or vegetables are selected from the list consisting of pepper, Tomato, eggplant, lettuce, zucchini and cucumbers and / or cereals are selected from a list consisting of rice, corn, wheat and rye. 43. The use of a coated fabric according to any of claims 1-25 or obtainable through the process according to claims 26-37 or 39 in plant crops and / or livestock animals to repel insects. 44. The use of a coated fabric according to the preceding claim to repel mosquitoes. 45. A kit comprising the following elements: - (i) a piece of coated fabric according to claims 1-25 or a fabric obtained through the process according to claims 26-39. - (ii) a box or container containing the piece of tissue according to item (i). - (iii) a brochure with instructions for use of the product for the treatment or prevention of diseases. 46. The use of the kit according to the preceding claim in the prevention and / or treatment of diseases caused by insects in crops and / or livestock animals and / or as a repellent against insects in plant crops or livestock animals. 47. A method for the prevention and / or treatment of diseases caused by insects or as a repellent against insects in crops comprising at least the steps: - Providing a piece of coated fabric according to any of claims 1-25 or the piece of fabric according to the kit according to claim 45; - Placing the piece of coated tissue according to any of claims 1 25 or the piece of tissue comprising the kit according to claim 45, in proximity or in contact with the agricultural crop that suffers a disease that can be prevented or treated with the compound I, compound II, compound III or with a mixture thereof, with at least one effective dose of said compounds, comprised in the tissue or in the kit. 48. The method of the preceding claim, wherein the crop is an agricultural or ornamental plant crop and where the insect pests are selected from the list consisting of Myzla, Drosophila suzukii, and Sitophilus zeamais 49. The kit according to claim 45 for use as an insect repellent in livestock animals and / or in plant crops 50. A method of repelling insect bites in livestock animals comprising at least the steps: - Providing a piece of coated fabric according to any of claims 1-25 or the piece of fabric according to the kit according to claim 45; - Placing the piece of coated tissue that comprises the kit according to claim 45, in proximity or in contact with the animal, wherein said tissue comprises an effective dose of compounds II or III. 51. The method of the preceding claim wherein the piece of tissue is placed around the neck of the animal or a device attached to the ear of the animal, said device being adapted to comprise said tissue or on the leg of the animal. 52. The method of the preceding claim wherein the device may be a tag or an elastic band. 53. The method according to claims 50-52 wherein the animal is selected from the list consisting of roof rack, sheep, pig, bull, horse, dog, cat, goat, ostrich. 54. The method according to claims 50-53, wherein the tissue can be left in contact or in proximity to the animal for at least 1 month.