AU2015308369A1 - Biocide and/or phytosanitary formulation for aerosol use, made of active biodegradable non-residual substances - Google Patents

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

1

BIOCIDE AND/OR PHYTOSANITARY FORMULATION FOR AEROSOL USE, MADE OF ACTIVE BIODEGRADABLE NON-RESIDUAL SUBSTANCES

DESCRIPTION

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a surface and environmental disinfecting system in the agri-food industry as well as in applications in veterinary science, domestic use, health care, institutional or industrial settings, as well as controlling post-harvest illnesses from vegetables and fruits by means of aerosol application systems, also known as cold fumigation or total discharge.

BACKGROUND OF THE INVENTION

In the state of the art there are several types of applications of formulations with disinfectant properties, such as biocides (fungicides, bactericides and/or virucides) and phytosanitary (understood as those applied to vegetables or fruits) properties for disinfecting environments and/or surfaces, as well as for controlling post-harvest illnesses from vegetables and fruits (acting as phytosanitary). Among them, smoke-producing containers or receptacles are worth mentioning as examples. However, the compositions used in these systems have various disadvantages such as their hazardous nature (due to being combustible) as well as the need for them to be lit on fire, which is associated with the creation of residues such as by-products of the combustion of the smoke producing components, such as, and mainly, due to the high temperatures that are generated, which means that many of the disinfecting, fungicidal or biocide products used cannot be used since they decompose under said conditions.

Currently, the biocides and phytosanitary products used in this task belong to chemical families that have been known for a long time (quaternary ammoniums, orthophenyl phenol, glutaraldehyde, iodine derivatives, chloride or peroxide derivatives, among others). These families of products are currently highly disputed for the following reasons: 1.- Cross-contamination problems: Active materials such as quaternary ammoniums or orthophenyl phenol, among others, have a persistence and residual effect that cause the disinfected products stored later or handled in facilities, chambers, shops, etc. to contain residues of said active materials.

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These residues bring with them a cross-contamination problem that means that they are frequently banned, particularly in the case of the agri-food industry. This implies that the affected products are rejected or cannot be sold/used, which is why they are no longer used in most of the facilities where they were used. 2. - Hazard and/or toxicity problems: Peroxides are corrosive, apart from the fact that in many instances they are not easy to apply. This means that the operator is exposed to their effects and risks, which means that in many kinds of applications (closed spaces, public places, etc.) their use is not viable. Other products, such as glutaraldehyde or other aldehydes like formaldehyde, have a very negative toxicological profile, which is why their uses are limited and even disappearing. The group of chloride derivatives, such as chloride itself, apart from the fact that in many kinds of applications it is not technically viable, also has the problem of creating by-products when it comes into contact with organic material (chloramines, among others). This implies that many of its applications are highly debated, and some of them are to be substituted, such as in the fruit, vegetable or pre-prepared food processing industry. 3. - Regulatory problems. Many of the active materials used in the field cannot meet the environmental and worker/consumer safety regulatory requirements in Europe and other countries. 4. - Due to the existing doubts with respect to the safety and crosscontamination residue problems, many sectors, mainly the agro-food sector, are banning their providers from using active materials with residue/toxic effects. 5. - There are other active materials that could be referred to as "traditional" that in certain conditions could be used but that, due to their characteristics (corrosiveness, hazard level, type of application), cannot be used in many conditions, such is the case of peracetic acid.

All of these constraints have meant that in some areas of human and industrial activity, the necessary disinfecting action has become so complicated that in some cases they do not have adequate means to carry it out.

Therefore, the development of active substances and application systems that can meet all of these needs is necessary, whilst fulfilling the previously explained requirements: harmlessness, absence of hazardous crosscontamination residue, absence of regulatory problems and low environmental impact (biodegradability), together with harmless application systems that 8788789J (GHMatters) P105366.AU 3 enable access to all the parts to be disinfected without exposing the applicator and without contamination risk from by-products or decomposition of the active material due to the heat (which biodegradable products tend to do), such as application systems using aerosol, cold fumigation or total discharge, all of which are synonyms.

It has been determined by scientists that the term AEROSOL defines a physical state. In a strict sense, it refers to a state of suspension of a large number of fine particles, solid or liquid enveloped in a gas, preferably air. The term comes 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 art has made use of several methods in order to generate true aerosols within a purely physical definition. The most recent method, and without a doubt the most "elegant" when reaching said objective, is carried out through liquid gases in a spray bottle under pressure. This method has become popular through aerosol containers for insecticides and deodorants, such that the term aerosol has been extended, also due to the lack of a general convenient term, to spraying and foaming with a propelling gas via pressurized gas containers. To this end, it should be indicated that in this way its original scientific meaning has been lost and, therefore, the imposed limit. This development has been favored by the fact that this term has been introduced in every language with no difficulty, such that it has come to be the international name. For this reason, everything that is related to the development, manufacturing and application of containers with pressurized gas is understood as being within the concept of "aerosol technology".

The art of aerosols is based on spraying a mix of the product to be made into a mist with a liquefied gas. Upon activating the valve, the expelled component of the liquefied gas evaporates in a very short time interval, "breaking up" the contained product. Considering the form of application, aerosol products can be subdivided into three different groups: a) Aerosols in a strict sense, through which the aim is to reach the finest possible distribution of the active substance and, as such, require the size of the particles of the spray jet to be as small as possible. Generally, the proportion of the active solution or suspension does not exceed, therefore, more than 20% by weight. These aerosols are used, for example, in inhalers, insecticides, air fresheners, etc.;

8788789 1 (GHMallers) P105366.AU 4 b) Those known by the generic name "surface sprays", which generate spray products whose particles are "coarser" and are used to dampen surfaces. These aerosols contain, referring to weight, approximately 30-60% active substance and are used, for example, in hairsprays, deodorants, cleaners, varnishes, sunscreens, etc.; and c) Aerosols with superficial effects, which generate products such as foam, whose particles are "coarse" and must carry out a superficial dampening function. These aerosols contain, referring to weight, between 30-60% active substance and are used, for example, in shaving creams, shampoos, cleaning foams, etc.

The active substance of the formulation can be differentiated in the following way: • Embodiments in which the active substance is constituted by a product dissolved in an organic solvent. In this case, the most common in the world of aerosols, the presence of water and the formation of a residue that contains 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 immiscible with water (oils) and the dispersion phase (internal) is constituted by water or an aqueous solution; • Embodiments in which the active substance is constituted by an aqueous solution of surfactant substances or by an emulsion solution of oil/water (which are mixed when the container is shaken); • Embodiments in which the active substance is constituted by a powdery substance (powder with the smallest particles possible); • Embodiments in which the active substance is constituted by an aqueous solution. These aerosols are called three-phase aerosols and have a reduced spraying effect.

Furthermore, the propellant is what makes the contents of the aerosol container exit through the valve. The aerosol can be used by means of a vaporizing push button or total discharge and can be filled like a conventional aerosol with its liquid and gaseous phases, or even by introducing the active substance through a "bag" system that consists of housing all the active material inside a bag and filling the space between the container and said bag with any type of compressed gas that acts as a propellant.

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Regarding the aerosol container, it is closely related to its predecessors, the carbonated water siphon and fire extinguishers. It is composed, therefore, of a pressure-resistant vessel and a valve that is joined by an ascending tube with the liquid that in turn is subjected to pressure by a gas. While in carbonated water siphon and fire extinguisher a compressed gas is used (generally carbon dioxide, C02) that is in the space for the gas above the liquid phase of the vessel, in the aerosol container instead of using a compressed gas propellant, liquefied pressurized gas is used, from which a series of advantages are derived, especially new possibilities in the art of applications, which will be described later.

Inventions aimed at designing aerosol formulations can be found in the patent literature. For example, the Australian patent application AU2012358872 describes methods and compositions for producing formulations intended for orally administered benzodiazepines.

As for RU2519653, it describes a formulation to be inhaled in the form of aerosol for treating bronchial asthma and chronic obstructive pulmonary disease.

It is common, therefore, to find aerosol formulations in the pharmaceutical industry or with medical purposes. However, until now there is no known project being developed of this type of formulation to be used in disinfection techniques for environments or surfaces, as well as for controlling post-harvest illnesses of vegetables and fruits. Furthermore, there is a need, which the present invention tries to solve, to have alternatives to the current techniques used in said applications, which entail the associated disadvantages states above.

DESCRIPTION OF THE INVENTION

The present invention therefore relates to an aerosol formulation (suitable to be applied in micronized form) characterized in that it comprises at least one biodegradable non-residual active substance with biocidal and/or phytosanitary effectiveness.

For the purposes of this patent, biocide is understood as any chemical substance of synthetic or natural origin used to destroy, counteract, neutralize, prevent the action of or exert a control of some kind over any organism considered harmful to man. Preferably, the active biocidal substance is a

8788789J (GHMatters) P105366.AU 6 substance with fungicidal, bactericidal and/or virucidal properties. Phytosanitary product is understood as any chemical substance of synthetic or natural origin used to destroy, counteract, neutralize, prevent the action of or exert a control of some kind over any organism considered harmful to plants (including vegetables and/or fruits).

The main advantage of the invention is, on the one hand, its harmlessness since it is based on a solution of an active substance that is driven out via a propellant that consists of at least a gas or mixture of gases at a suitable pressure and, on the other hand, how, since it may be applied in a micronized form, it is capable of reaching areas that other types of applications (sprays, washing, etc.) cannot reach since they are not accessible to the same.

With respect to the choice of the active substance, as was mentioned, it must have enough disinfectant properties (biocide and/or phytosanitary) and simultaneously has to combine properties like biodegradability, absence of residual effects and low toxicity and hazard levels. Sufficient disinfectant properties are established as those that accomplish at least a 50% reduction of the initial contamination.

In a particular embodiment of the invention, said substance can consist of a food additive with preserving characteristics (disinfecting), which may be sorbic acid and the salts thereof, calcium propionate, benzoic acid and the salts thereof, such as, in general, any of those included in the positive list of additives, potassium sorbate being especially preferred for its characteristics of lack of toxicity and residual effect, as well as for its biodegradability and effectiveness in disinfection. Once the suitable additive is selected it is necessary to elaborate the appropriate aerosol formulation that fulfills the adequate 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 vegetable 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 those mentioned, the use of glycolic acid (also known as hydroxyacetic acid) is preferred due to its high effectiveness and its positive authorization and registration (regulatory) conditions, as well as its biodegradability and absence of cross residual effects. Another type of substances, such as alcohols (ethanol, propanol, glycols, etc.) could be used in this kind of applications, even though 8788789J (GHMatters) P105366.AU 7 they are less preferred products. In particular, said substances can be used together with the aim of, for example, helping to dissolve the active substance during the aerosol preparation process.

In this way, several aerosol formulations have been developed, with bases of food additives (preferably potassium sorbate), natural extracts and/or acids of vegetable origin (preferably glycolic or hydroxyacetic acid), that can be combined with other active substances or with other additives (such as deodorizers).

As indicated previously, the active substance is dissolved in a suitable solvent, preferably in a percentage by weight less than 60%. Said solvent may be chosen between water, alcohol or other solvents (such as glycols, non-polar hydrocarbons, polar hydrocarbons, etc.) or an azeotrope of at least two solvents (for example, water and alcohol) Additionally, the solution may comprise other substances such as surfactants (preferably anionic or no ionic surfactants) or other substances with wetting or defoaming power, such as fatty alcohols or other ethoxylated active materials.

Preferably, the active substance is comprised in the formulation in a percentage by weight comprised between 20 and 60% and even more preferably between 10 and 30% by weight.

As a propellant of the formulation it is possible to use at least a liquefied gas, understood as a substance that at room temperature (25°C) and atmospheric pressure are gaseous and, as the pressure is increased, they are compressed into a vapor form until reaching the saturation limit, such that, by increasing the compression further, the gas finally condenses into liquid form. The condensation into liquid phase 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 can consist of halogenated hydrocarbons of low global warming potential (GWP) (preferably below 100 and more preferably below 50) such as HFO 1234 ze.

All the gases whose critical temperature is lower than the normal room temperature (25°C), such as nitrogen, oxygen, air, hydrogen or noble gases, cannot be liquefied at room temperature and therefore must be used as compressed gases. This type of gases can also be used as particular 8788789J (GHMatters) P105366.AU 8 embodiment of the invention, in which case the normal pressure range inside the aerosol is from 2 to 18 kg/cm2.

There is a series of substances whose boiling point is below room temperature, its critical temperature being sufficiently above room temperature. This implies that they can be liquefied below pressures that are not too elevated, generally less than 10 kg/cm2. From a purely physical point of view, all these gases could be used in aerosol technology. However, for safety reasons, gases that are toxic or that, such as certain hydrocarbons, must be considered with caution from a physiological point of view cannot be used. An additional limitation comes from the combustibility of a great number of gases and their property of forming, even in low concentrations, explosive mixtures.

Preferably it is possible to use safe propellants, which include for example halogenated hydrocarbons or fluorinated gases. Safe propellants are understood as not being combustible or toxic and because they do not irritate the mucous membranes either. Furthermore, they are odorless and, from a chemical point of view, are extraordinarily stable.

The liquefied gas selected as a propellant has to carry out various functions in the aerosol container. Each liquefied gas ha a very precise vapor pressure at a certain temperature. This physical law is compiled in the vaporization tables and vapor graphs. The vapor pressure changes with relative intensity with the temperature. At the same temperature, the vapor pressure of the gases varies individually. This means that an intermediary value of vapor pressure can be established, if desired, through mixtures of gases and liquids with liquefied gases. The vapor pressure is, therefore, dependent on the temperature and on the composition of the liquid phase and does not change when the liquid is slowly consumed by its outlet through the ascending tube and the valve or push button of the aerosol vessel. This is due to the fact that the necessary amount of vapor is always formed from the liquid phase in order to keep the pressure constant in the vaporization space, each time more than the last, until the last drop of liquid is consumed.

In this way, the propellant can be selected, preferably, from a group that consists of a compressed gas, preferably at least a diatomic gas such as nitrogen or oxygen, among others; at least one hydrocarbon of any kind such as pentane, butane or propane, among others, or at least a liquefied organic gas such as dimethyl ether, as well as any combination thereof. Specifically, the 8788789J (GHMatters) P105366.AU 9 combinations of compressed gases with liquefied gases are known in the art as cocktails. Particularly, the hydrocarbon may consist of at least one halogenated hydrocarbon with low GWP such as HFO 1234 ze.

Generally, the propellant is comprised in the formulation in a percentage 5 by weight between 40 and 80% and more preferably between 50 and 60% by weight.

Below, examples are shown of preferred embodiments of the formulation object of the invention, in any case the active substances being substances with disinfectant properties, biodegradable and without risk of cross-contamination, 10 which can be in certain conditions and applications combined with common disinfectants, with the aim of increasing the synergetic effect of said products. The percentages in bold are the weights with respect to the formulation and the percentages not in bold are the weights with respect to the propellant or to the active substance solution, respectively: 15

Formulation 1 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Potassium sorbate or other fungistatic additive >0-45% Water 0-70% Alcohols 0-70%

Formulation 2 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60%

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Orthophenyl phenol or other phenols >0-45% Water 0-30% Alcohols 0-80% Defoamer 0-5% Anionic surfactants 0-80%

Formulation 3 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liguefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Glycolic acid or other acids >0-45% Water 0-70% Alcohols 0-70%

Formulation 4 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liguefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Quaternary ammoniums >0-45% Water 0-70% Alcohols 0-70%

Formulation 5 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50%

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Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Glutaraldehyde or other aldehyde or disinfectant >0-45% Water 0-70% Alcohols 0-70%

Formulation 6 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Potassium sorbate or other fungistatic additive >0-45% Glycolic acid or other acids 0-20% Water 0-70% Alcohols 0-70%

Formulation 7 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Potassium sorbate or other fungistatic additive >0-45% Quaternary amines 0-40% Water 0-70% Alcohols 0-70%

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Formulation 8 PROPELLANT 40-80% Compressed gas (preferably a diatomic gas) 0-50% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0-70% Halogenated hydrocarbons with low GWP 0-100% Liquefied organic gases 0-100% ACTIVE SUBSTANCE SOLUTION 20-60% Orthophenyl phenol or other disinfectants >0-45% Phenylphenol Salt >0-45% Water 0-30% Alcohols 0-80% Defoamer 0-5% Anionic surfactants 0-80%

Below are examples of especially, but not limiting, preferred embodiments of 5 the invention:

Formulation 9 PROPELLANT 50% Compressed gas (preferably a diatomic gas) 0% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 5% Halogenated hydrocarbons with low GWP 0% Liquefied organic gases 95% ACTIVE SUBSTANCE SOLUTION 50% Potassium Sorbate 25% Water 30% Alcohols 45%

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Formulation 10 PROPELLANT 53% Compressed gas (preferably a diatomic gas) 0% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 0% Halogenated hydrocarbons with low GWP 100% Liquefied organic gases 0% ACTIVE SUBSTANCE SOLUTION 47% Orthophenyl phenol 19.90% Water 0% Alcohols 79.90% Defoamer 0.20% Anionic surfactants 0%

Formulation 11 PROPELLANT 50% Compressed gas (preferably a diatomic gas) 0% Hydrocarbons (without including halogenated hydrocarbons with low GWP) 5% Halogenated hydrocarbons with low GWP 0% Liquefied organic gases 95% ACTIVE SUBSTANCE SOLUTION 50% glycolic acid 10% Water 36% Alcohols 54% 5 As indicated, the aerosol formulation is contained in a container that has a closing or sealing system and a suitable nozzle that provides the micronization properties in the use of the aerosol. When the seal is broken, it lets out the active substance solution through the nozzle and driven by the propellant. The special design of the nozzle means that the solution of the 10 active substance is applied with micronized drops (micron sized), creating a mist that enables the active substance to reach all the areas to be disinfected.

Apart from the lid and the final labeling, the most important elements of the aerosol container are:

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On one hand, the container in itself, which may be made from various materials: tin, aluminum, reinforced glass, plastic covered glass, PET, etc., and be of various shapes, even though the most used are: aluminum monobloc container, two-element container with a flanged bottom and three-element container with assembled lid and flanged bottom. Furthermore, those finished in tin and aluminum can have a varnish for interior protection that protects the vessel from the possible aggression of the product it contains. The choice of the type of container, obviously, depends on the chemical composition of the active substance to be contained.

And, furthermore, the valves. The purpose of the valve is to accurately regulate the amount of the contents to be expelled from the vessel. Likewise, it must act such that the size of the particles is uniform and the spray effect homogeneous. The valve not only comprises the push button that is pressed for the discharge, but also its interior mechanism, which is composed of: support for the valve, joints, basic tube or push button, head and cannula or ascending tube.

The different types of valves that can be used also depend on the product to be expelled through the same. In this way, there are several kinds of valves: • One-shot valves, all the contents of the container exit to the exterior at once after being activated; • Normal pressure valves, which are activated by pressing vertically on the head and they automatically close when the pressing stops; • Valves activated via rocker arm which are opened by pressing laterally on the push button and frequently they do not have an installed spring, but are pushed up by an elastic point back to its original vertical position; or • Dispensing valves, which are pressure valves but in which only a certain amount of the content is expelled when the push button is pressed, the stream then being interrupted.

Preferably in the case of the present invention, standard 1" (2.54 cm) valves will be used, either male or female, and 1" (2.54 cm) total or dispensing discharge valves.

Finally, the method of application of the aerosol formulation previously defined, in environment and on surfaces, is likewise an additional object of the

8788789J (GHMallers) P105366.AU 15 invention. In the case of being applied in large volumes or rooms (such is the case with storage tanks) the use of fans is recommended during its application, with the aim of reaching a more homogeneous distribution.

During the application of the aerosol formulation, the liquid phase reaches the atmosphere through the ascending tube and the valve of the aerosol container, due to the excess pressure of the vapor that comes from pressing the push button, instantly producing the evaporation of the liquid propellant (as there is no excess pressure). Thus, it is not possible to recover the state of aggregation of the expanded gas. In the 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 consequence of the spontaneous evaporation of the propellant. The greater the proportion of the propellant, the finer the spray in the liquid phase will be and, on the other hand, smaller the proportion of the propellant, the less gas will be contained, thus being able to be reduce the liquid phase from exiting as a compact stream. This last aspect coincides with the known process of carbonated sodium water, through which the proportional part of dissolved gas in the liquid is greatly reduced, such that the stream that exits is practically compact.

At the other end, when the content of the propellant is elevated, the spray grade can be increased, such that the particles of active substance fluctuate in the air and, therefore, form an aerosol within the original strict scientific sense of the term.

Thus, it is possible to adjust and achieve all kinds of sprays, from a practically compact stream to a finer grade of spray/mist.

In particular embodiments, it is possible to create a foam arranged to be used immediately. This is possible when the liquid of the aerosol container is not miscible with the product or active substance, even though it can form a dispersed emulsion phase. In this way, upon activating the push button of the aerosol vessel, the contents exit as a foam. This is due to the fact that in the container it is found distributed in the product in the form of very fine drops, each one forming a bubble as it evaporates, the totality of which constitutes the foam.

Generally, the liquid (solvent or mixture of solvents) acts as a vehicle for the active substance per se. There is also the possibility of dissolving the active substance, whether it be directly, or dispersed in the same. In this way, the 8788789J (GHMatters) P105366.AU 16 propellant is directly converted into a vehicle of the filling spray substance, such as in the case of the powder or in the inhalation of certain pharmaceutical products.

In the case of embodiments in which the propellant comprises compressed gases, said gases will not be able to carry out the functions described previously related to the liquefied gases. The difference is based on the fact that the compressed gases practically do not dissolve in the liquids of the different filling substances. Their function is therefore fundamentally limited to maintaining the internal pressure, while the liquids dissolved in reduced quantities cannot expect more than a crude or rough spray.

The propelling compressed gases can be organized into two groups, concerning their solubility in liquid filling products: a) Practically insoluble gases, such as air, nitrogen or noble gases; and b) Gases with a limited solubility, such as diazo monoxide (nitrogen oxide, laughing gas, N2O) or carbon dioxide (CO2).

The solubility of these propelling gases is different with regards to the type of liquids that enter into consideration.

The pressure of the propelling compressed gases changes very little with the temperature. On the contrary, the internal pressure goes down as the consumption of the liquid load goes up, since the volume of the space for the gas increases several times in relation to the original volume. In this way, as the space for the gas doubles, the absolute pressure of a compressed gas goes down by half, and as the volume of the gas triples, the absolute pressure goes down to a third of the original value.

As such, for example, in a vessel filled with 2/3 liquid and a compressed gaseous phase at a pressure of 6.5 atm (equivalent to approx. 7.5 kp/cm2 absolute pressure), said pressure will start to go down as the liquid starts to exit the vessel, reducing the volume of the gaseous phase to 2.5 kp/cm2 absolute pressure.

The excess pressure in the vessel can therefore change during the consumption from 6.5 atm to 1.5 atm, in other words, going below ΛΜ of the original percentage value. A certain solubility of the gas in the liquid somewhat reduces this pressure drop. However, the considerable pressure decrease during its use imposes strict limits on the compressed gases. All leakage in the gaseous phase and any inadequate handling, due to an excessive inclination of 8788789J (GHMallers) P105366.AU 17 the container such that the end of the submerged tube is situated in the gaseous phase upon activating the push button, lead to considerable gas losses. Especially in this last case, almost all the gas frequently leaks out, such that the product is useless. The loss of gas cannot be substituted in this case for the liquid phase, since the solubility of the compressed gas is insufficient, including, in the second group corresponding to the gases with limited solubility.

The main advantages of the present invention, therefore, come from the use of aerosol technology, which is preferably based on the use of safe liquefied agents. This technology leads to a series of advantages and has, above all, a large number of possible applications. In this way, the following advantages must be highlighted, which also apply to the case of the present invention: • Every aerosol container is an automatic device that allows for extracting or applying the product in the most convenient form so as reach an optimal effect through pressing on the push button with the finger. Through this activation with the push button it can distribute the amount of the product to be applied with greater ease and in a more rational way than pouring the liquids. Where applying a constant and equal dose is suitable, the dispensing valve assumes the quantitative limiting function; • The automatism of the aerosol container makes other products or auxiliary means unnecessary in many cases, such as the use of fine brushes, manual injectors, sprayers or large brushes for creating foam. In this way, it makes it possible to obtain foam that is ready to be used immediately, as well as supplying a finely sprayed product. The convenience of handling this kind of automatic push button cannot be surpassed. They are practical, simple and clean; • The automatic closing valve means that the contents do not escape or pour out. The liquid substances do not evaporate and the contents do not dry out. The seal of the container prevents air and possible impurities due to dust, humidity or germs from entering. In this way, oxidizable products can be used since the oxygen in the air practically will not come into contact with the same; • For the application of many products, the fact that the pressurized spraying makes a cheap and uniform spread on the object possible, without the need to enter into contact with it, constitutes a great

8788789_1 (GHMatters) P105366.AU 18 advantage.

Among other applications, without being limiting, their use for disinfecting environments and/or surfaces, as well as for controlling illnesses of post-harvested vegetables and fruits may be cited. In addition to the agri-food industry, it also has applications in veterinary science, domestic use, health care, institutional or industrial settings, etc., all of these based on the use of aerosol application systems, also known as cold fumigation or total discharge.

Due to the fact that in some disinfections, the application conditions are in closed spaces, this causes the treatments of the invention to have many particularities that distinguish them from the usual disinfecting treatments. Fundamentally, apart from the point of view of toxicity, adverse conditions arise, such as the impossibility of cleaning, accumulation of bad odors, excess of contaminating load, etc. For which, it can be beneficial: • To add a harmless substance that helps eliminate smell, it could be a flavoring or perfume, such as limonene: • For some special markets, such as the meat, dairy, cheese industries, etc. in which there are important contamination problems due to bacteria that are harmful to man, but at the same time there is the limitation of residual effects on the handled products. The use in combination of distinct active substances is especially preferred, which can be potassium sorbate, glycolic acid or other vegetable extracts or aldehydes and acids of vegetable origin, forming a "cocktail" or mixture of disinfectants capable of increasing the activity spectrum of each active substance separately; • When necessary, in serious cases, these active biodegradable substances can be combined in the aerosol with classic active substances, such as orthophenyl phenol, glutaraldehyde or quaternary ammoniums, in low concentrations, with the aim of applying a shock disinfection, leaving the lowest level of residue possible. • Lastly, in cases in which there are no problems of residual effects or environmental impact, the use of the aerosols of the invention could be complementary to the use of other non-biodegradable substances, increasing their activity spectrum.

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BRIEF DESCRIPTION OF THE DRAWINGS

Fig 1 Aerosol container, having: (1) Valve (push button) (2) Vessel (3) Gaseous (propellant force of the aerosol container) (4) Active substance mixture (liquid) (5) Ascending tube

Fig 2 Application of aerosols in chambers;

Fig 3 1 liter aerosol container for the complete discharge of cold spray;

Fig 4 Graph showing the reduction of the microbial load in the environment (Number of colonies in the total number of exposed dishes), according to example 1. The column on the left (138, 44) corresponds to the initial number of colonies and the column on the right (49, 17) corresponds 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 dishes), according to example 1. The column on the left (396, 176) corresponds to the initial number of colonies and the column on the right (217, 160) corresponds to the number of colonies after treatment;

Fig 6 Image of one of the two aerosols when initiating the disinfection of a 400 m3 chamber, in which two 1-liter aerosol containers were applied;

Fig? Environment disinfection in the 400 m3 chamber, in which two 1-liter aerosol containers were applied. Initial contamination;

Fig8 Environment disinfection of the 400 m3 chamber, in which two 1-liter aerosol containers were applied. Contamination 24 h after treatment;

Fig 9 Disinfection of surfaces in the 400 m3 chamber, in which two 1-liter aerosol containers were applied. Initial contamination;

Fig 10 Disinfection of surfaces in the 400 m3 chamber, in which two 1-liter aerosol containers were applied. Contamination 24 h after treatment;

Fig 11 Distribution of the four aerosol containers in an 800 m3 chamber, in which four 1-liter aerosol containers were applied;

Fig 12 Environment disinfection in the 800 m3 chamber, in which four 1-liter aerosol containers were applied. Initial contamination;

8788789_1 (GHMatters) P105366.AU 20

Fig 13 Environment disinfection in the 800 m3 chamber, in which four 1-liter aerosol containers were applied. Contamination 24 h after treatment;

Fig 14 Disinfection of surfaces in the 800 m3 chamber in which four 1-liter aerosol containers were applied. Initial contamination;

Fig 15 Disinfection of surfaces in the 800 m3 chamber, in which four 1-liter aerosol containers were applied. Contamination 24 h after treatment;

Fig 16 Application of aerosol in the container;

Fig 17 Aerosol for complete discharge of cold spray;

Fig 18 Reduction of microbial load on surfaces. The column on the left (228, 149) corresponds to the initial number of colonies and the column on the right (196, 100) corresponds to the number of colonies after treatment;

Fig 19 Reduction of microbial load in the room. The column on the left (42, 20) corresponds to the initial number of colonies and the column on the right (178, 11) corresponds to the number of colonies after treatment;

Fig 20 Reduction of microbial load on surfaces. The column on the left (39, 15) corresponds to the initial number of colonies and the column on the right (36, 5) corresponds to the number of colonies after treatment;

Fig 21 Images of treatment 1 of an aerosol of 500 ml of 5%. Environment disinfection. The image on the left corresponds to the initial contamination and the image on the right corresponds to the contamination 24 h after the treatment;

Fig 22 Images of treatment 1 of an aerosol of 500 ml of 5%. Disinfection of surfaces. The image on the left corresponds to the initial contamination and the image on the right corresponds to the contamination 24 h after the treatment.

DEMONSTRATION OF THE EFFECTIVENESS OF THE FORMULATION IN EXAMPLE 1

The test was done in empty refrigerated chambers which had contained citrus fruit in commercial refrigerators.

Two chambers with different capacities (400 m3 and 800 m3) were used and the degree of initial contamination due to both fungi and bacteria on the

8788789_1 (GHMatters) P105366.AU 21 surface of the walls and in the environment was analyzed. Six environment dishes and six contact dishes were used.

The aerosols of potassium sorbate were then applied with the ventilation unit running for 30 minutes so that the ventilator would be able to properly disperse the entire product, and the air vents of the air circulation system were covered. The product was left to act for 24 hours (the chambers remained closed the entire time), and samples of the environment and the surfaces were then taken to determine the reduction in contamination of fungi and bacteria, thereby measuring the effect of the treatment. Six environment dishes and six contact dishes were used.

Fig. 2 shows an image of the application of the aerosols in the chambers.

Each aerosol used has a capacity of 1000 ml and contains 750 ml of a mixture of gases and the product, of which 375 ml is a potassium sorbate solution at 25% (93.8 g of potassium sorbate in each bottle). In this test, a single dose of treatment was studied, one liter of aerosol for every 200 m3 of the chamber, which was applied in two different sized chambers: • 400 m3 chamber: two 1 -liter aerosol containers were applied • 800 m3 chamber: four 1 -liter aerosol containers were applied

Fig. 3 shows a 1 liter aerosol container for the complete discharge of cold spray.

RESULTS

Effectiveness of disinfection

As can be seen in the table, the dose used had a disinfection effectiveness of just almost 70%, although the average for the two chambers was approximately 66%. As for the disinfection of surfaces, an average effectiveness of just under 41% was achieved, although the effectiveness appears to be greater the smaller the chamber to be disinfected. DOSE SIZE OF THE EFFECTIVENESS OF DISINFECTION CHAMBER ROOM SURFACES One 1-liter aerosol 800 m3 65.3 % 26.3 % container / 200 m3 400 m3 68.1 % 55.0 % AVERAGE 66.7 % 40.7 %

8788789_1 (GHMatters) P105366.AU 22

Fig. 4 shows a chart with the results of the reduction in the microbial load in the room, and Fig. 5 shows a chart with the results of the reduction in the microbial load on surfaces.

Fig. 6 shows an image of one of the two aerosols when initiating the disinfection of a 400 m3 chamber, in which two 1-liter aerosol containers were applied.

Fig. 7 shows the initial contamination in different areas of the 400 m3 chamber (left, door and right) in the test for environment disinfection.

Fig. 8 shows the contamination 24 hours after treatment in different areas of the 400 m3 chamber (left, door and right) in the test for environment disinfection.

Fig. 9 shows the initial contamination in different areas of the 400 m3 chamber (left, door and right) in the test for surface disinfection.

Fig. 10 shows the contamination 24 hours after treatment in different areas of the 400 m3 chamber (left, door and right) in the test for surface disinfection.

Fig 11 shows the distribution of the four aerosols in an 800 m3 chamber, in which four 1 -liter aerosol containers were applied.

Figure 12 shows the initial contamination in different areas of the 800 m3 chamber (central area, back area and door area) in the test for environment disinfection.

Fig. 13 shows the contamination 24 hours after treatment in different areas of the 800 m3 chamber (central area, back area and door area) in the test for environment disinfection.

Figure 14 shows the initial contamination in different areas of the 800 m3 chamber (door area, central area, back area) in the test for surface disinfection.

Fig. 15 shows the contamination 24 hours after treatment in different areas of the 800 m3 chamber (door area, central area and back area) in the test for surface disinfection. EXAMPLE 2

The test was done in refrigerated truck containers of a transport refrigeration company.

Four clean containers with a capacity of 87.3 m3 were used and the

8788789J (GHMallers) P105366.AU 23 degree of initial contamination due to both fungi and bacteria on the surface of the walls and in the environment was analyzed.

Aerosols of potassium sorbate were then applied with the refrigeration running for 30 minutes so that the ventilator would be able to properly disperse the entire product, and the product was left to act for 24 hours (the containers remained closed the entire time), and samples of the environment and the surfaces were then taken once more to determine the reduction in the contamination of fungi and bacteria, thereby measuring the effectiveness of the treatment.

Fig. 16 shows an image of the application of the aerosol in the truck container.

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

Fig. 17 shows an image of the aerosol container for the complete discharge of cold spray.

RESULTS

Effectiveness of disinfection DOSE Original formulation Environment disinfection Wall disinfection 1 aerosol 68.2 % 34.6 % 2 aerosols 74.3 % 49.0 %

As can be seen in the table, with the treatments of 1 and 2 bottles, a disinfection effectiveness of approximately 70% was obtained for the environment, which was even greater when two bottles were applied (which constitutes twice the dose)._

Fig. 18 shows a chart with the results of the reduction in the microbial load in the application to surfaces, before and after the treatment. EXAMPLE 3. Evaluation of the effectiveness of a glycolic-acid-based aerosol (cold fumigation, total discharge).

The results obtained were the following: 8788789_1 (GHMatters) P105366.AU 24 DOSE Size of the chamber Effectiveness of disinfection Environment Surfaces 1 aerosol of 5% 10 m3 52.4 % 61.5 % 1 aerosol of 10% 10 m3 93.8 % 86.1 %

As can be seen, the effectiveness obtained was very high in the case of the aerosol of 10%, equivalent to the disinfection of a residual disinfectant. 5 Fig. 19 shows a chart with the results of the reduction in the microbial load in the room, before and after the treatment.

Fig. 20 shows a chart with the results of the reduction in the microbial load in the application to surfaces, before and after the treatment.

Fig. 21 and Fig. 22 show images of the treatment with an aerosol of 500 10 ml of 5% (on the left the images of the initial contamination are shown, and on the right, 24 hours after the treatment). Specifically, Fig. 21 shows the images of the treatment of environment disinfection and Fig. 22 shows the images of the treatment of surface disinfection.

Conclusions 15 Based on the preceding examples, it may be concluded that the application of the invention using aerosol with the base of a biodegradable substance and without a residual effect (for example, glycolic acid), has shown an effectiveness equivalent to that which is obtained by common disinfectants, although it has all of the previously described advantages associated with its 20 application through aerosol.

8788789J (GHMallers) P105366.AU

Claims (11)

1. An aerosol formulation having biocide and/or phytosanitary properties characterized in that it comprises: (a) 20 to 60% by weight of a solution of at least an active biodegradable substance having biocide and/or phytosanitary properties; (b) 40 to 80% by weight of at least a propellant.

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

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

4. The formulation according to claim 2 or 3, wherein the acid of vegetable origin is glycolic acid.

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

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

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

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

9. An aerosol container characterized in that it comprises an automatic closing valve and in that it contains a formulation according to any one of the claims 1 to 8.

10. A use of a formulation according to any one of the claims 1 to 8 for disinfecting environments and/or surfaces by applying the formulation in the form of an aerosol.

11. The use of a formulation according to any one of the claims 1 to 8 for controlling post-harvest illnesses from vegetables and/or fruits by applying the formulation in the form of an aerosol.