WO2016030555A1

WO2016030555A1 - Biocide and/or phytosanitary formulation for aerosol use, made of active biodegradable non-residual substances

Info

Publication number: WO2016030555A1
Application number: PCT/ES2015/070496
Authority: WO
Inventors: Francisco ALBEROLA CLAVER; Enrique Gómez Hernández; Mar LLUECA JUESAS; Yolanda SANCHIS SILLA; Jorge Eugenio MASIP GARCÍA
Original assignee: Decco Ibérica Post Cosecha, S.A.U.; Maldoni Shop, S.L.
Priority date: 2014-08-27
Filing date: 2015-06-25
Publication date: 2016-03-03
Also published as: CN107105644A; AU2015308369A1; ES2561933A1; ES2561933B2; CN107105644B; AU2015308369B2; ZA201701820B

Abstract

The invention relates to a formulation having biocide and/or phytosanitary properties that is used the form of aerosol, characterized in that said formulation comprises: (a) 20 to 60% by weight of a solution of at least an active biodegradable substance having biocide and/or phytosanitary properties; and (b) 40 to 80% by weight of at least a propellant. An aim of the invention is also to use said formulation to disinfect rooms and/or surfaces, as well as to control illnesses from post-harvest vegetables and/or fruits by using the formulation in the form of an aerosol.

Description

BIOCIDE AND / OR PHYTOSANITARY FORMULATION OF APPLICATION IN THE FORM OF AEROSOL BASED ON NON-RESIDUAL BIODEGRADABLE ACTIVE SUBSTANCES DESCRIPTION

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a system of environmental and surface disinfection both in the agri-food industry and in applications in veterinary, domestic, sanitary, institutional or industrial use, as well as the control of post-harvest diseases of fruits and vegetables through use of aerosol application systems, also known as cold fumigation or total discharge. BACKGROUND OF THE INVENTION

In the state of the art there are different types of applications of formulations with disinfectant properties, that is, biocides (fungicides, bactericides and / or virucidal) and phytosanitary (understood as being applied on vegetables, vegetables or fruits) for the disinfection of environments and / or surfaces, as well as for the control of post-harvest diseases of vegetables, fruits and vegetables (acting as phytosanitary). Among them, it is possible to mention, for example, the fumigant containers or cans. However, the compositions used in these systems have several disadvantages such as their danger (being oxidizing), as well as the need for them to be ignited under flame, which is associated with the generation of waste as products of combustion of the components used for the production of smoke, as well as, and mainly, because of the high temperatures that are generated, which means that many of the disinfectant, fungicide or biocidal products used cannot be used because they decompose under these conditions. Currently the biocides and phytosanitary products used in this task belong to chemical families that have been well known since ancient times (quaternary ammoniums, orthophenylphenol, glutaraldehyde, iodine derivatives, chlorinated derivatives or peroxides, among others). These families of products are currently very questioned for the following reasons: 1.- Cross-contamination problems: Active substances such as quaternary ammoniums or orthophenylphenol, among others, have a persistence and a residual effect that makes the products subsequently stored or manipulated in facilities, cameras, premises, etc. disinfected, residues of said active materials appear. These residues entail a problem of cross-contamination that frequently means that, especially in the case of the agri-food industry, they are not admitted. This implies that the affected products are rejected or cannot be commercialized / used, so that in most of the facilities where they were used they have been discontinued.

2. - Danger and / or toxicity problems: Peroxides are corrosive, and in many cases they are not easy to apply. This implies that the operator is exposed to its effects and risks, which means that in many types of applications (enclosures, public premises, etc.) its application is not viable. Other products, such as glutaraldehyde or other aldehydes such as formaldehyde, have a very negative toxicological profile, so their uses are being limited and even disappearing. The group of chlorinated derivatives, such as chlorine itself, in addition to the fact that in many types of applications they do not have technical feasibility, they also present the problem of the generation of by-products in contact with organic matter (chloramines, among others). This implies that many of its applications are being questioned, and it is directly intended to replace them in some of them, such as in the fruit, vegetable or fourth range processing industry.

3. - Regulatory problems. Many of the active materials used in the technique cannot meet the environmental and safety requirements of the regulatory worker and consumer in Europe and other countries. 4.- Due to existing doubts regarding safety and cross-contamination waste problems, many sectors, mainly agri-food, are prohibiting their suppliers from using disinfectants of active materials with residual / toxic effect. 5.- There are other active materials that we could call "traditional" that in some conditions could be used but that, due to their characteristics (corrosivity, danger, type of application), cannot be used in many conditions, such as acid Peracetic All these conditions have meant that in some areas of human and industrial activity, the necessary disinfection action has been complicated in such a way that even in some cases there are no adequate means for its realization. Therefore, it is necessary to develop active substances and application systems that can meet all these needs, in compliance with the requirements explained above: safety, absence of hazardous waste due to cross contamination, absence of regulatory problems and low environmental impact (biodegradability ), together with innocuous application systems that allow access to all parts to be disinfected without exposure of the applicator and in the absence of contamination risks due to by-products, or decomposition of the active material by heat (to which the products tend biodegradable), such as aerosol application, cold spraying (total fumigation) or total discharge systems, all synonymous with them.

The term AEROSOL has been determined by scientists to define a physical state. Strictly speaking it refers to a state of suspension of a large number of fine, solid or liquid particles within a gas, preferably air. The term derives from the words aero (from Greek, in the air), and solutio (from Latin, solution). This means a colloidal solution of non-gaseous substances in the air. The technique has used different methods to generate true aerosols within pure physical definition. The most recent and undoubtedly the most "elegant" method of achieving this objective is developed using liquid gases from a spray container under pressure. This method has been popularized by aerosol containers for insecticides and deodorants, such that the term aerosol has been extended, also due to the lack of a convenient general term, to spraying and foaming with a propellant gas by means of gas containers. Pressure. In this sense, it is to indicate that, in this way, its original scientific meaning and, therefore, the limit imposed have been lost. This development has been favored by the fact that this term has been introduced without any difficulty in all languages, so that it has become the international denomination. For this reason it is understood under the concept "aerosol technology" everything that is related to the development, manufacture and application of containers with gas under pressure.

The aerosol technique is based on spraying a mixture of the product to be sprayed with a liquefied gas. When the valve is operated, the expelled component of the liquefied gas evaporates in a very short time, "tearing" the contained product. In consideration of the form of application, aerosol products can be subdivided into three different groups:

a) Aerosols in the strict sense, through which it is intended to achieve The finest possible distribution of the active substance and, therefore, requires keeping the particle size of the spray jet as small as possible. Generally, the proportional part of the active solution or suspension does not therefore exceed more than 20% by weight. These aerosols are used, for example, in inhalers, insecticides, air fresheners, etc .;

Those known under the generic designation of "surface sprays", which generate spray products whose particles are more "coarse" and are used to wet surfaces. These aerosols contain, based on weight, approximately 30-60% of active substance and are used, for example, in hairspray, deodorants, polishers, varnishes, sunscreens, etc .; Y

Surface effect aerosols, which generate foam-like products, whose particles are "coarse" and must perform a surface moisturizing function. These aerosols contain, based on weight, between 30-60% of active substance and are used, for example, in shaving foams, shampoos, detergent foams, etc.

The active substance of the formulation can be differentiated as follows:

Embodiments in which the active substance is constituted by the product dissolved in an organic solvent. In this case, the most common in the aerosol world, the presence of water and the formation of a residue containing water are avoided as much as possible;

Embodiments in which the active substance is constituted by a water / oil emulsion. In this case, the external phase is constituted by an organic liquid not miscible with water (oils) and the dispersed (internal) phase is constituted by water or an aqueous solution;

Embodiments in which the active substance is constituted by an aqueous solution of surfactants or by an oil / water emulsion solution (which are mixed when the content is stirred);

. Embodiments in which the active substance is constituted by a pulverulent substance (powder with particles of the smallest possible size);

Embodiments in which the active substance is constituted by an aqueous solution. They are called three-phase aerosols and have a reduced spray effect.

On the other hand, the propellant is what causes the contents of the aerosol container to flow through the valve. The aerosol can be used by vaporization by pulsation or total discharge and can be filled as a conventional aerosol with its liquid and gaseous phases or by introducing the active substance from a "bag" system that consists of housing all the active matter inside a bag and filling the space between the container and said bag with any type of compressed gas that acts as a propellant.

As for the aerosol container, it has a lot to do with its predecessors, the siphon and the fire extinguisher. It consists, therefore, of a pressure-resistant container and a valve that is connected by an ascending tube with the liquid which in turn is subjected to pressure by a gas. While a compressed gas (usually carbon dioxide, C0 ₂ ) is used in the siphon and fire extinguisher that is in the gas space above the liquid phase of the container, instead of the aerosol container of compressed propellant gas, a gas under liquid pressure, from which a series of advantages and, in particular, new possibilities in the application technique are derived, as will be described later.

In patent literature it is possible to find inventions aimed at designing aerosol formulations. Thus, for example, in the Australian patent application AU2012358872 a method and composition for producing formulations intended for oral administration of benzodiazepines is described.

RU2519653, meanwhile, describes a formulation to be inhaled as an aerosol in the treatment of asthma and chronic lung diseases. It is therefore common to find aerosol formulations in the pharmaceutical industry or for medical purposes. However, no development project of this type of formulations to be used in environmental or surface disinfection techniques, as well as for the control of post-harvest diseases of fruits and vegetables is known to date. On the other hand, there is a need, to which the present invention tries to solve, to present alternatives to the current techniques used in said applications, which have the aforementioned drawbacks associated.

DESCRIPTION OF THE INVENTION

The present invention therefore relates to an aerosol formulation (suitable for being applied in a micronized form) characterized in that it comprises at least one biodegradable and non-residual active substance with biocidal and / or phytosanitary efficacy. For the purposes of this patent, biocide is understood as any synthetic or natural chemical substance intended to destroy, counteract, neutralize, prevent the action or exercise control of any other type on any organism considered harmful to man. Preferably, the biocidal active substance will be a substance with fungicidal, bactericidal and / or virucidal properties. As a phytosanitary product, any synthetic or natural chemical substance is intended to destroy, counteract, neutralize, prevent the action or exert control of any other type on any organism considered harmful to plants (including vegetables, fruits and / or vegetables).

The main advantage of the invention lies on the one hand in its safety, since it is based on a solution of an active substance that is propelled abroad by means of a propellant (or propellant) consisting of at least one gas or mixture of gases at a suitable pressure and, on the other, in which as a consequence of being able to be applied in a micronized way, it is capable of reaching areas that other types of applications (spraying, washing, etc.) cannot reach by not being accessible to same. Regarding the choice of the active substance, as mentioned, it must have sufficient disinfectant properties (biocides and / or phytosanitary) and simultaneously it must combine biodegradability properties, absence of residual effect and low toxicity and danger. As sufficient disinfectant properties are established those that meet the order of at least 50% reduction of the initial contamination.

In a particular embodiment of the invention, said substance may consist of a food additive with preservative characteristics (disinfectants), such as sorbic acid and its salts, calcium propionate, benzoic acid and its salts, as well as, in general, any of those included in the positive list of additives, potassium sorbate being especially preferred for its characteristics of absence of toxicity and residual effect, as well as for its biodegradability and good disinfection efficiency. Once the appropriate additive has been selected, it will be necessary to develop the appropriate aerosol formulation that meets the appropriate characteristics according to its application, as will be explained later.

In another particular embodiment of the invention, the active substance may consist of a substance of natural origin, such as an acid of plant origin (glycolic acid, citric acid or acetic acid, among others) or a natural extract (such as cinnamic aldehyde, eugenol, thymol or carvacrol, among others). Of all of the above, due to its high efficiency and its positive conditions of authorization and registration (regulatory), as well as its biodegradability and absence of crossed residual effects, the use of glycolic acid (also known as hydroxyacetic acid) will be preferred. Other substances, such as alcohols (ethanol, propanol, glycols, etc.) could also be used in this type of applications, although they are products of less preferred use. In particular, said substances can be used in conjunction with the purpose, for example, of helping to dissolve the active substance during the aerosol preparation process.

In this way, different aerosol formulations have been developed, based on food additives (preferably potassium sorbate), natural extracts and / or acids of plant origin (preferably glycolic or hydroxyacetic acid), which can be combined with other active substances or with other additives (such as deodorizers). As indicated above, the active substance is dissolved in a suitable solvent, preferably in a weight percentage of less than 60%. Said solvent may be selected from water, alcohol or other solvents (such as glycols, non-polar hydrocarbons, polar hydrocarbons, etc.) or an azeotrope of at least two solvents (such as water and alcohol, for example). Additionally, the solution may comprise other substances such as surfactants (preferably anionic or non-ionic surfactants) or other substances with wetting or antifoaming power such as fatty alcohols or other ethoxylated active substances. Preferably, the active substance is comprised in the formulation in a weight percentage between 20 and 60% and more preferably between 10 and 30% by weight.

As the propellant (or propellant) agent of the formulation it is possible to use at least one liquid gas, understanding as such that substance that under ambient temperature (25 ° C) and atmospheric pressure are gaseous and, when the pressure increases, they are compressed in the form of steam until it reaches the saturation limit, so that, further increasing compression, the gas finally condenses as a liquid. Liquid phase condensation is only possible at a temperature below the critical temperature of the gas. Examples of liquid (or liquefied) gases are hydrocarbons such as isobutane, propane, pentane or butane, among others, or liquefied organic gases, such as dimethyl ether. Preferably, the hydrocarbons may consist of halogenated hydrocarbons of low global warming potential (GWP) (preferably below 100 and more preferably below 50) such as HFO 1234 ze. All gases whose critical temperature is below normal ambient temperature (25 ° C), such as nitrogen, oxygen, air, hydrogen or noble gases, cannot liquefy at room temperature and therefore must be used as gases tablets This type of gas can also be used as a particular embodiment of the invention, in which case the usual range of pressure inside the aerosol is from 2 to 18 kg / cm ² .

There are a number of substances whose boiling point is below room temperature, their critical temperature being sufficiently above room temperature. This implies that they can be liquefied under pressures not too high, generally less than 10 kg / cm ² . From a purely physical point of view, all these gases could be used in aerosol technology. However, for safety reasons, those gases that are toxic or that, like certain hydrocarbons, must be considered with physiological reserves cannot be used. An additional limitation results from the combustibility of a large number of gases and their property of forming, even at very low concentrations, explosive mixtures.

Preferably, it is possible to use safety propellants (or propellants), among which are, for example, halogenated hydrocarbons or fluorinated gases. They are understood as propellant safety agents because they are neither combustible nor toxic and because they do not cause irritation of the mucous membranes. In addition, they are odorless and, from a chemical point of view, they are extraordinarily stable.

The liquefied gas selected as a propellant must fulfill several functions in the aerosol container. Each liquefied gas has a very precise vapor pressure at a certain temperature. This physical law is compiled in vaporization tables and steam graphs. Vapor pressure varies with relative intensity with temperature. At the same temperature, the vapor pressure of the gases varies individually. This implies that an intermediate, desired value of vapor pressure can be established through mixtures of gases and liquids with liquefied gases. The vapor pressure is therefore dependent on the temperature and composition of the liquid phase and does not vary when the liquid is gradually consumed by its exit through the riser and the valve or pulsator of the aerosol container. This is because the necessary amount of steam is always formed from the liquid phase in order to always keep the pressure in the vaporization space constantly increasing, until the last drop of liquid is consumed.

In this way, the propellant can preferably be selected from a group consisting of a compressed gas, preferably at least one diatomic gas such as nitrogen or oxygen, among others; at least one hydrocarbon of any type such as pentane, butane or propane, among others, or at least one liquefied organic gas such as dimethyl ether, as well as any combination thereof. Specifically, combinations of compressed gases with liquefied gases are known in the art as cocktails. In particular, the hydrocarbon may consist of at least one halogenated hydrocarbon of low GWP such as HFO 1234 ze.

In general, the propellant is comprised in the formulation in a weight percentage of between 40 and 80% and more preferably between 50 and 60% by weight. Examples of preferred embodiments of the formulation object of the invention are indicated below, the active substances being in any case substances with disinfectant properties, biodegradable and without risks of cross contamination, which may be in certain conditions and applications combined with usual disinfectants, in order to increase the synergistic effect of these products. The percentages in bold are by weight with respect to the formulation and the percentages not highlighted are by weight with respect to the propellant or the active substance solution, respectively:

Formulation 1

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas) Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Potassium sorbate or other fungistatic additive> 0-45%

Water 0-70%

0-70% alcohols

Formulation 2

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Orthophenylphenol or other phenols> 0-45%

Water 0-30%

0-80% alcohols

Defoamer 0-5%

0-80% anionic surfactants

Formulation 3

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Glycolic acid or other acids> 0-45%

Water 0-70%

0-70% alcohols Formulation 4

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Quaternary ammonia> 0-45%

Water 0-70%

0-70% alcohols

Formulation 5

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Glutaraldehyde or other aldehyde or> 0-45% disinfectant

Water 0-70%

0-70% alcohols

Formulation 6

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Potassium Sorbate or other fungistatic additive> 0-45% Glycolic acid or other 0-20% acids

Water 0-70%

0-70% alcohols

Formulation 7

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Potassium Sorbate or other fungistatic additive> 0-45%

Quaternary amines 0-40%

Water 0-70%

0-70% alcohols

Formulation 8

PROPELLENT 40-80%

Compressed gas (preferably a 0-50% diatomic gas)

Hydrocarbons (not including halogenated 0-70% low GWP hydrocarbons)

Low GWP halogenated hydrocarbons 0-100%

Liquefied organic gases 0-100%

DISSOLUTION OF ACTIVE SUBSTANCE 20-60%

Orthophenylphenol or other disinfectants> 0-45%

Phenylphenol salt> 0-45%

Water 0-30%

0-80% alcohols

Defoamer 0-5%

0-80% anionic surfactants

Examples of especially preferred, but not limiting, embodiments of the invention are set forth below: Formulation 9

PROPELLENT 50%

Compressed gas (preferably a 0% diatomic gas)

Hydrocarbons (not including 5% halogenated low GWP hydrocarbons)

Halogenated hydrocarbons of low GWP 0%

95% liquefied organic gases

DISSOLUTION OF ACTIVE SUBSTANCE 50%

25% Potassium Sorbate

Water 30%

Alcohols 45%

Formulation 10

PROPELLENT 53%

Compressed gas (preferably a 0% diatomic gas)

Hydrocarbons (not including halogenated 0% low GWP hydrocarbons)

Halogenated hydrocarbons of low GWP 100%

Liquefied organic gases 0%

DISSOLUTION OF ACTIVE SUBSTANCE 47%

Orthophenylphenol 19.90%

0% water

Alcohols 79.90%

0.20% defoamer

0% anionic surfactants

Formulation 11

PROPELLENT 50%

Compressed gas (preferably a 0% diatomic gas)

Hydrocarbons (not including 5% halogenated low GWP hydrocarbons)

Halogenated hydrocarbons of low GWP 0%

95% liquefied organic gases

DISSOLUTION OF ACTIVE SUBSTANCE 50% 10% glycolic acid

Water 36%

Alcohols 54%

As indicated, the aerosol formulation is contained in a container consisting of a closure or seal system and a suitable nozzle that provides micronization properties in the use or use of the aerosol. When the seal is broken, the solution of the active substance is expelled through the nozzle and driven by the propellant. The special design of the nozzle causes the solution of the active substance to be applied with a micronized drop size (the size of microns), producing a mist that allows the active substance to reach all areas of the area to be disinfected.

In addition to the cap and the final labeling, the most important elements of the aerosol container are the following:

On the one hand, the container itself, which can be of various materials: tin, aluminum, reinforced glass, plastic coated glass, PET, etc., and in different forms, although the most used are: monobloc aluminum container , two-element container with flanged bottom and three-element container with assembled lid and flanged bottom. In addition, tin and aluminum finishes can be presented with a varnish for internal protection that protects the container from possible aggression of the product it contains. The choice of the type of package will obviously depend on the chemical composition of the active substance to be packaged.

And, on the other hand, the valves. The purpose of the valve is to regulate exactly the amount of content to be ejected from the container. It must also act in such a way that the particle size is uniform and the effect of homogeneous spraying. The valve not only comprises the button that is pressed for discharge, but also its internal mechanism, which is composed of: valve support, seals, basic or push-button tube, head and cannula or riser tube. The different types of valves that can be used will also depend on the product to be expelled through it. There are several types of valves in this way:

One-shot valves, after actuation of which all the contents of the container go outside at once; Normal pressure valves, which are actuated by a vertical oppression in the head and close automatically when the oppression ceases;

Rocker-actuated valves, which are opened by lateral oppression of the button and often do not have an installed spring, but are compressed back by an elastic tip to its original vertical position; or

Dosing valves, which are pressure valves but in which, when compressing its button, only a certain amount of the content is expelled, the jet being interrupted below. Preferably, in the case of the present invention, standard 1 "valves, either male or female, and 1" full discharge or metering valves will be used.

Finally, the method of application of the aerosol formulation defined above, both in the environment and on surfaces, is also a further object of the invention. In case of being applied in large volumes or environments (as is the case of storage chambers) it is recommended to use fans during their application, in order to achieve a more homogeneous distribution. During the application of the aerosol formulation the liquid phase, due to the overpressure of the steam that originates when the button is pressed, reaches the atmosphere through the ascending tube and the valve of the aerosol container, instantaneously producing the evaporation of the liquid propellant agent (when there is no overpressure). In this way, it is not possible to recover the aggregation state of the expanded gas. In those embodiments in which the liquid phase is constituted by a mixture of propellant and active substance, the liquid formed by the active substance is sprayed or atomized as a result of spontaneous evaporation of the propellant. The higher the proportion of the propellant, the finer the spray will be in the liquid phase and, conversely, the lower the proportion of the propellant, the lower the gas content, which can be reduced so that the liquid phase leaves as a compact jet. This last aspect coincides with the well-known process of the sodium water siphon, whereby the proportional part of the gas dissolved in the liquid is very small, so that the jet that comes out is practically compact.

At the other end, when the propellant agent content is high, the degree of spraying can be increased, such that the substance particles active fluctuating in the air and, consequently, forming an aerosol within the strict original scientific sense of the term.

In this way, it is possible to graduate and achieve all kinds of sprays, from a practically compact jet to the finest degree of fogging.

In particular embodiments it is possible to generate a foam arranged to be used immediately. This is possible when the liquid in the aerosol container is not miscible with the active product or substance, although it may form a dispersed emulsion phase. In this way, when the button of the aerosol container is operated, the content thereof is foam-shaped. This is due to the fact that in the package it is distributed in the product in the form of very fine drops, each of which, upon evaporation, forms a bubble, the whole of which constitutes the foam. In general, the liquid (solvent or solvent mixture) acts as a vehicle for the active substance itself. There is also the possibility of dissolving the active substance, either directly, or dispersed therein. In this way, the propellant becomes directly the carrier of the filler spray substance, as is the case, for example, in the case of dust or in the inhalation of certain pharmaceutical products.

In the case of those embodiments in which the propellant agent comprises compressed gases, said gases will not be in a position to fulfill the functions described above relating to liquefied gases. The difference is based on the fact that the compressed gases do not dissolve, practically, in the liquids of the different fillers. Its function is therefore limited, fundamentally, to the maintenance of internal pressure, while liquids dissolved in small quantities cannot be expected more than a coarse or coarse spray. Compressed propellant gases can be ordered in two groups, in terms of their solubility in liquid fillers:

a) Virtually insoluble gases, such as air, nitrogen or noble gases; and b) Gases with limited solubility, such as diazoic monoxide (nitrogen protoxide, hilarious gas, N ₂ 0) or carbon dioxide (C0 ₂ ).

The solubility of these propellant gases is different in regard to the type of liquids that come into consideration. The pressure of compressed propellant gases varies very little with temperature. On the contrary, the internal pressure drops with the increasing consumption of the liquid load, since the volume of the gas space increases several times in relation to the original volume. Thus, when the gas space is doubled, the absolute pressure of a compressed gas drops in half, and when the gas volume triples, the absolute pressure drops to one third of the original value.

Thus, for example, in a container filled with 2/3 of liquid and a compressed gas phase at a pressure of 6.5 atm (equivalent to approx. 7.5 kp / cm ² of absolute pressure), said pressure will decrease as it goes the liquid leaving the container, decreasing the volume of the gas phase to 2.5 kp / cm ² absolute pressure.

The overpressure in the container can therefore vary during consumption from 6.5 atm to 1.5 atm, that is, falling below ¼ of the original value. A certain solubility of the gas in the liquid somewhat reduces this pressure drop. However, the considerable decrease in pressure during use imposes very narrow limits on compressed gases. Any leakage in the gas phase and any improper handling, due to excessive inclination of the container so that the end of the submerged tube is located in the gas phase when the button is operated, lead to considerable gas losses. Especially in the latter case, almost all of the gas is frequently leaked, so that the product is unusable. The loss of gas cannot be replaced in this case by the liquid phase, since the solubility of the compressed gas is insufficient, even in the second group corresponding to gases of limited solubility.

The main advantages of the present invention thus derive from the use of aerosol technology, which is preferably based on the use of liquefied safety agents. This technology leads to a number of advantages and has, above that, a large number of application possibilities. In this regard, the following advantages should be highlighted, which also apply to the case of the present invention:

Every aerosol container is an automatic device that allows the product to be extracted or applied in the most convenient way in order to achieve an optimal effect through an oppression with the finger on the button. The amount of the product to be applied more easily and more rationally than when pouring liquids can be distributed with this button. Where is it indicated to apply a constant and equal dose, the dosing valve assumes the quantitative limiting function;

The automatism of the aerosol container makes unnecessary, in many cases, other products or auxiliary means, such as the use of brushes, manual injectors, sprayers or brushes to generate foam. In this way, it makes it possible to obtain foam ready for immediate use, as well as to supply a fine powdered product. The convenience of handling this type of automatic pushbuttons cannot be exceeded. They are practical, simple and clean;

The automatic shut-off valve does not leak or tip the contents. Liquid substances do not evaporate and the content does not dry out. The tightness of the container prevents the entry of air and possible impurities by dust, moisture or germs. In this way, oxidizable products can be used since the oxygen in the air will practically not come into contact with them;

. For the application of many products, the fact that pressure spraying allows an economic and uniform extension on the object, without the need to come into contact with it, is a great advantage.

Among other applications, without being limiting, its use can be cited for the disinfection of environments and / or surfaces, as well as for the control of post-harvest diseases of vegetables, fruits and / or vegetables. In addition to the agri-food industry, it will also have applications in veterinary, domestic, sanitary, institutional or industrial use, etc., all based on the use of aerosol application systems, also known as cold spraying. fumigation) or total discharge.

Because in some disinfections the application conditions are in closed enclosures, this makes the treatments of the invention have many peculiarities that distinguish them from the usual disinfectant treatments. Fundamentally, apart from the toxicity point of view, adverse conditions are given to them, such as the impossibility of cleaning, accumulation of bad odors, excess pollutant load, and so on. Therefore, it can be beneficial:

Add a harmless substance that helps eliminate odor, such as flavorings or perfumes, such as limonene;

. For some special markets, such as the meat, dairy, cheese, etc. industries, where there are important problems of contamination by bacteria harmful to man, but at the same time there is the limitation of residual effects on the products handled, it may be especially preferred the use in combination of different active substances, such as potassium sorbate, glycolic acid or other plant extracts or aldehydes and acids of plant origin, forming a "cocktail" or mixture of disinfectants capable of increasing the spectrum of activity of each active substance separately;

If necessary, and of great severity, these biodegradable active substances in the aerosol can be combined with classic active substances, such as orthophenylphenol, glutaraldehyde or quaternary ammoniums, at low concentrations, in order to exert a shock disinfection leaving the minimum level possible residual;

Finally, in cases where there are no problems of residual effects or environmental impact, the use of the aerosols of the invention may be complementary to the use also in aerosol of other non-biodegradable active substances, increasing their spectrum of activity.

BRIEF DESCRIPTION OF THE FIGURES

Fig 1 Aerosol container, where:

(1) Valve (push button)

(2) Container

(3) Gaseiform (propelling force of the aerosol container)

(4) Active substance mixture (liquid)

(5) Ascending tube

Fig 2 Application of aerosols in the chambers;

Fig 3 1 liter full discharge spray for cold fogging;

Fig 4 Graph showing the reduction of the microbial load in the environment (Number of colonies in the total number of exposed plates) according to example 1. The left column (138, 44) corresponds to the initial number of colonies and the right column (49, 17) to the number of colonies after treatment;

Fig 5 Graph showing the reduction of the microbial load on surfaces (Number of colonies in the total number of exposed plates) according to example 1. The left column (396, 176) corresponds to the initial number of colonies and the column from the right (217, 160) to the number of colonies after treatment; Image of one of the two aerosols at the start of disinfection in a 400 m ³ chamber to which 2 aerosols of 1 liter are applied;

Environmental disinfection in the 400 m ³ chamber to which 2 aerosols of 1 liter are applied. Initial contamination;

Environmental disinfection in the 400 m ³ chamber to which 2 aerosols of 1 liter are applied. Pollution 24 h after treatment;

Disinfection of surfaces in the 400 m ³ chamber to which 2 aerosols of 1 liter are applied. Initial contamination;

Disinfection of surfaces in the 400 m ³ chamber to which 2 aerosols of 1 liter are applied. Pollution 24 h after treatment;

Distribution of the four aerosols in an 800 m ³ chamber to which 4 aerosols of 1 liter are applied;

Environmental disinfection in the 800 m ³ chamber to which 4 aerosols of 1 liter are applied. Initial contamination;

Environmental disinfection in the 800 m ³ chamber to which 4 aerosols of 1 liter are applied. Pollution 24 h after treatment;

Disinfection of surfaces in the 800 m ³ chamber to which 4 aerosols of 1 liter are applied. Initial contamination;

Disinfection of surfaces in the 800 m ³ chamber to which 4 aerosols of 1 liter are applied. Pollution 24 h after treatment;

Application of the aerosol in the container;

Full discharge spray for cold fogging;

Reduction of microbial load on surfaces. The left column

(228, 149) corresponds to the initial number of colonies and the right column (196, 100) to the number of colonies after treatment;

Reduction of microbial load in the environment. The left column (42,

20) corresponds to the initial number of colonies and the right column (178,

1 1) to the number of colonies after treatment;

Reduction of microbial load on surfaces. The left column (39, 15) corresponds to the initial number of colonies and the right column

(36, 5) to the number of colonies after treatment;

Images per treatment 1 of a 500 ml spray of 5%. Environmental disinfection The image on the left corresponds to the initial contamination and the one on the right to the contamination 24 hours after the treatment;

Images per treatment 1 of a 500 ml spray of 5%. Surface disinfection. The image on the left corresponds to the initial contamination and the one on the right corresponds to the contamination 24 hours after the treatment. DEMONSTRATION OF THE EFFECTIVENESS OF THE FORMULATION

EXAMPLE 1

The test was carried out in empty cold rooms that had citrus content in commercial refrigerators.

Two chambers of different capacities (400 m ³ and 800 m ³ ) were used and the degree of initial contamination due to both fungi and bacteria on the surface of the walls and in the environment was analyzed. Six room plates and six contact plates were used.

The potassium sorbate aerosols were then applied, with the ventilation equipment running for 30 minutes for the fan to properly distribute the entire product, and with the air renewal grilles covered. The product was allowed to act for 24 hours (the chambers remained closed all that time), after which environment and surface samples were taken again to determine the reduction of fungal and bacterial contamination, thus measuring the effectiveness of the treatment . Six room plates and six contact plates were used.

An image of the application of aerosols in the chambers is shown in Fig. 2. Each aerosol used has a capacity of 1000 ml and contains 750 ml of a mixture of gases and product, of which 375 ml is a 25% potassium sorbate solution (93.8 g of potassium sorbate in each canister). In this test, a single dose treatment, 1 spray 1 liter per 200 m ³ chamber was studied and applied in two sizes different camera:

- 400 m ³ chamber: 2 aerosols of 1 liter were applied

800 m ³ chamber: 4 sprays of 1 liter were applied

A full-discharge 1 liter spray for cold fogging is shown in Fig. 3. RESULTS

Efficacy of disinfection As can be seen in the table, with the dose used an efficiency in the disinfection of the environment of almost 70% can be achieved, although the average of the two chambers is approximately 66%. Regarding surface disinfection, an average efficiency of almost 41% has been obtained, although it seems to be more effective when the chamber to be disinfected is smaller.

In Fig. 4 a graph is shown with the results of the reduction of the microbial load in the environment and in Fig. 5 a graph is shown with the results of the reduction of the microbial load on surfaces.

In Fig. 6 the image of one of the two aerosols at the start of disinfection is shown in a 400 m ³ chamber to which 2 aerosols of 1 liter are applied. The initial contamination in different areas (left, door and right) of the 400 m ³ chamber in the environmental disinfection test is shown in Fig. 7.

In Fig. 8 the contamination is shown 24 hours after treatment in different areas of the 400 m ³ chamber (left, door and right) in the environmental disinfection test.

The initial contamination in different areas (left, door and right) of the 400 m ³ chamber in the surface disinfection test is shown in Fig. 9. In Fig. 10 the contamination is shown 24 hours after treatment in different areas (left, door and right) of the 400 m ³ chamber in the surface disinfection test.

The distribution of the four aerosols in an 800 m ³ chamber to which 4 aerosols of 1 liter are applied is shown in Fig. 1 1; The initial contamination in different zones (central zone, bottom zone and door zone) of the 800 m ³ chamber in the environmental disinfection test is shown in Fig. 12.

In Fig. 13, the contamination is shown 24 hours after treatment in different areas of the 800 m ³ chamber (central zone, bottom zone and door zone) in the environmental disinfection test. In Fig. 14 the initial contamination in different zones (door zone, central zone and bottom zone) of the 800 m ³ chamber in the surface disinfection test is shown.

In Fig. 15 the contamination is shown 24 hours after the treatment in different zones (door zone, central zone and bottom zone) of the 800 m ³ chamber in the surface disinfection test.

EXAMPLE 2 The test was carried out in refrigerated truck containers of a refrigerated transport company.

4 clean containers, of 87.3 ^m3 capacity were used and the degree of initial contamination due both fungi as bacteria on the surface of the walls and the environment was analyzed.

The potassium sorbate aerosols were then applied, with the cold running for 30 minutes for the fan to properly distribute the entire product, and allowed to act for 24 hours (the containers remained closed all that time), after which were taken again samples of environment and surfaces to determine the reduction of contamination by fungi and bacteria, thus measuring the effectiveness of the treatment.

An image of the application of the aerosol in the container is shown in Fig. 16.

Each aerosol has a capacity of 500 ml_ and contains 400 ml_ of a mixture of gases and product, of which 200 ml is 25% potassium sorbate solution (50 g of potassium sorbate in each pot). In this trial, two treatment doses, 1 or 2 bottles per container, were studied.

An image of the complete discharge spray for cold fogging is shown in Fig. 17.

RESULTS

Efficacy of disinfection

As can be seen in the table, with treatments with 1 and 2 bottles, an efficiency in the disinfection of the environment of about 70% is obtained, being greater when 2 boats are applied (which is twice the dose).

A graph showing the results of the reduction of the microbial load in the application on surfaces, before and after the treatment is shown in Fig. 18.

EXAMPLE 3. Evaluation of the effectiveness of an aerosol (cold fumigation, total discharge) based on glycolic acid

The results obtained were the following:

As can be seen, the efficiency obtained has been very high in the case of the 10% aerosol, equivalent to the disinfection of a residual disinfectant. A graph showing the results of the reduction of the microbial load in the environment is shown in Fig. 19, before and after the treatment. A graph is shown in Fig. 20 with the results of the reduction of microbial load on surfaces, before and after treatment.

In Fig. 21 and in Fig. 22, images of the treatment with a 500 ml aerosol of 5% are shown (on the left the images of the initial contamination are shown and on the right, 24 h after the treatment). Specifically, Fig. 21 shows the images of the environmental disinfection treatment and Fig. 22 shows the images of the surface disinfection treatment.

Conclusions

From the previous examples it can be concluded that the application of the invention as an aerosol based on a biodegradable substance and without residual effect (in the example, glycolic acid), has been shown to have an efficacy equivalent to that obtained from the usual disinfectants, although it has all the advantages described above associated with its application as an aerosol.

Claims

1. Aerosol formulation with biocidal and / or phytosanitary properties characterized by comprising:

(a) between 20 and 60% by weight of a solution of at least one biodegradable active substance with biocidal and / or phytosanitary properties;

(b) between 40 and 80% by weight of at least one propellant or propellant.

2. Formulation according to claim 1, wherein the active substance is selected from a group consisting of a food additive, an acid of plant origin and a natural extract, as well as any combination thereof.

3. Formulation according to claim 2, wherein the food additive is potassium sorbate.

4. Formulation according to claim 2 or 3, wherein the acid of plant origin is glycolic acid.

5. Formulation according to any one of the preceding claims, characterized in that it comprises a second active substance selected from a group consisting of orthophenylphenol, glutaraldehyde and at least one quaternary ammonium, as well as any combination thereof.

6. Formulation according to any one of the preceding claims, wherein the active substance is in solution in a weight percentage of less than 60% by weight and wherein said solution comprises at least one solvent selected from a group consisting of water, alcohol and an azeotrope formed by a mixture of water and alcohol.

7. Formulation according to any one of the preceding claims, wherein the propellant or propellant consists of a compressed gas and / or a liquid gas selected from at least one hydrocarbon and a liquefied organic gas, as well as any combination thereof.

8. Formulation according to claim 7, wherein the hydrocarbon is a halogenated hydrocarbon with low global warming potential.

9. Aerosol container characterized in that it comprises an automatic shut-off valve and that it contains a formulation according to any one of claims 1 to 8.

10. Use of a formulation according to any one of claims 1 to 8 for the disinfection of environments and / or surfaces by application in aerosol form.

1 1. Use of a formulation according to any one of claims 1 to 8 for the control of post-harvest diseases of vegetables, fruits and / or vegetables by application in the form of an aerosol.