RU2360702C2 - Fume-forming compositions based on didecyldimethylammonium halogenide and their application for disinfection and/or disinfection - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: pyrotechnic composition for obtaining of didecyldimethylammonium halogenide aerosol contains didecyldimethylammonium halogenide or its clathrate with urea as active substance and the thermic composition providing the sublimation of the active substance during combustion. The invention refers also to the fume-forming pyrotechnic article, to the method for disinfection and/or disinfection of the objects as well as to the method for protection of the objects from biological damage at storage.

EFFECT: efficient disinfection and disinfection, protection of the objects from biological damage at storage together with low consumption of the active substance and low aerosol toxicity.

38 cl, 1 dwg

Description

Field of Invention

The invention relates to means and methods for disinfection and disinsection. In particular, the invention relates to pyrotechnic compositions which contain, as an active ingredient, a quaternary ammonium compound, such as didecyldimethylammonium halide. The invention relates to methods for disinfection and disinsection using highly dispersed aerosols generated by the combustion of said pyrotechnic composition.

The invention provides means and methods for disinfecting objects, including air, in agriculture, food industry, medicine, public utilities, transport, as well as to eliminate foci of infection and disinfection.

State of the art

The disinfecting action of quaternary ammonium compounds, in particular didecyldimethylammonium halide, is known in the art. Didecyldimethylammonium halides are known as chlorides, iodides and fluorides. In practice, the most common is didecyldimethylammonium bromide, which is often used in the form of a clathrate with urea (urea). Urea didecyldimethylammonium clathrate is a compound containing 30% by weight of didecyldimethylammonium bromide and 70% urea.

Didecyldimethylammonium halides, like their clathrates, are odorless crystalline powder. These compounds have surface-active properties, are readily soluble in water. Their melting point is about 150 ° C. At the melting point, didecyldimethylammonium halides and their clathrates do not decompose. With an increase in temperature, partial decomposition of the compounds takes place, the viscous melt foams, intensive vapor evolution takes place, and then, as the temperature rises further, coking of the residue occurs. In a medium containing oxygen, at a temperature substantially exceeding the melting point, the boiling didecyldimethylammonium halide or its clathrate ignites and burns with almost no residue.

Didecyldimethylammonium halide and its clathrate have a bactericidal, bacteriostatic, fungicidal, virucidal effect (RU 2158141, EA 000113). In addition, it was reported that urea didecyldimethylammonium bromide clathrate was used in pesticidal and repellent compositions as an additional substance used in conjunction with a saturated cyclic compound (RU 2221424). However, there is no evidence that didecyldimethylammonium halide or its urea clathrate has insecticidal activity per se. The source RU 2158141 indicates the possibility of using solutions containing didecyldimethylammonium halide clathrate with urea to disinfect volumes by spraying and irrigation.

RU 2214837 discloses a disinfectant based on didecyldimethylammonium clathrate urea bromide, containing hydroxyacid, inorganic salt and a water-soluble excipient as additives to ensure effective disinfection. Thus, this source suggests that the disinfecting properties of didecyldimethylammonium halide are enhanced in an acidic environment. In addition, it is known that an increase in the disinfecting activity of didecyldimethylammonium halide occurs when aldehydes are introduced into the solution. This approach is implemented in a number of commercial preparations, for example, the Tricidicide preparation (manufacturer: Meddezpharm LLC), which includes 16% didecyldimethylammonium chloride, 12% glutaraldehyde, as well as anti-corrosion additives and surfactants, pH 5.4 ± 1. Compositions of similar composition are marketed under various names.

Didecyldimethylammonium halides or didecyldimethylammonium halide clathrates with urea (urea) are used mainly in the form of dilute solutions, since a medium with a high degree of water content is necessary for disinfection, and the disinfection mechanism assumes that it is carried out through the surface-active properties of quaternary ammonium compounds. Reported bactericidal activity of highly concentrated solutions of Quaternary ammonium bases, i.e. at their concentrations substantially higher than the concentration of micelle formation in the prior art is not found.

Thus, the prior art focuses on the use of dilute solutions that contain didecyldimethylammonium halide or its clathrate with carbamide as an active substance, with some additives that activate its action, when disinfected by soaking, irrigation or wiping.

On the other hand, prior art methods for disinfection and disinfection using aerosols. Aerosols are dispersed systems consisting of small particles suspended in a gaseous medium. The use of aerosols ensures the penetration of suspended particles into hard-to-reach areas. Aerosol particles after deposition have high adhesion to the surface. Due to the large specific surface area of the particles, they are highly reactive, and are also characterized by high mass transfer between the particles and the gas phase.

Aerosol treatment makes it possible to make the process of disinfection or disinfection of volumes, premises and objects located in them more technological. The traditional method consists in irrigation and wiping of surfaces, objects and equipment with subsequent exposure, involves significant time and labor costs. Moreover, irrigation and wiping of large areas, objects with internal cavities, surfaces with a microporous structure (concrete, wood, plaster), animal processing, etc., are of particular difficulty. Traditional methods allow you to apply the active substance only on accessible external surfaces. Due to capillary phenomena, surface tension and the phenomenon of wettability, the disinfectant does not penetrate into the depths of most developed surfaces, which are the accumulation of pathogens. In this regard, in practice there is a significant overspending of existing funds. Based on the need for guaranteed disinfection, the principle of “fill everything” is implemented in practice, which ultimately leads to economic losses associated with both the cost of disinfection and the cost of restoring the facility to its original or operational state (if possible or necessary).

To overcome the disadvantages of traditional disinfection methods, an aerosol or volumetric disinfection method has been developed.

But, despite the fact that the effectiveness of the use of aerosols for disinfection was proved back in the mid-80s, it was not implemented in practice due to the lack of the necessary equipment and effective and cheap reagents that maintain their activity in the aerosol state.

The method is based on the principle of converting liquid disinfectants into highly dispersed aerosols. Aerosol is formed, as a rule, when using pneumatic or mechanical atomizers of liquids. An aerosol quickly fills the air of enclosed spaces inside rooms, containers or spreads over an open area, penetrating into inaccessible places and condenses in the form of a thin film on the surface of cavities and microscopic surface irregularities. An important condition for effective action on the surface is air humidity and temperature gradient, i.e. the difference in temperature of the disinfectant and surfaces. The higher the air humidity and the higher the temperature of the disinfectant compared to the temperature of the treated surfaces, the faster the condensation of aerosol fog on the surfaces. When using the aerosol method, high efficiency is achieved due to the fact that the aerosol, having great penetrating ability, disinfects not only surfaces, but also the air in the room, which can also be significantly contaminated. In this case, the consumption of disinfectants is reduced in comparison with the wet processing method, since when spraying the substance into the smallest particles, the area of the active surface of the drug sharply increases.

Thus, in the prior art, it is recognized that aerosol disinfection is an effective and economical method both in terms of drug consumption and labor costs.

Aerosol preparations based on hydrogen peroxide, formaldehyde, glutaraldehyde are traditionally used for aerosol disinfection. There are no reports of disinfection or disinsection with highly dispersed aerosols of solid surfactants, such as quaternary ammonium compounds per se, in the prior art. The existing reports on the use of surfactants in liquid compositions used in the form of aerosols for disinfection suggest their auxiliary role as wetting agents, moisturizers, activators of oxidizing agents, as agents that support the moisture content of liquid aerosol particles, etc., but do not suggest their use as an independent active substance intended to neutralize the contaminant.

Two groups of aerosol formation methods are known from the prior art: dispersion and condensation.

Various dispersion agents are used for dispersion, and aerosols with a liquid dispersed phase are usually obtained, where the particles consist of a solution of a dispersible substance. Upon receipt of condensation aerosols, the dispersed phase is formed on the condensation nuclei upon cooling of gaseous products below their boiling point.

Condensation aerosols are characterized by a smaller particle size than dispersion aerosols. Small particles are characterized by a higher specific surface area and greater sedimentation stability. Condensation aerosols have, as a rule, a particle size not exceeding 5-10 microns, while for dispersive aerosols the lower limit of particle sizes is about 20 microns. In this regard, it is generally accepted that condensation aerosols are more reactive.

For disinfection, as already mentioned, dispersion aerosols are traditionally used. The use of both dispersive and condensation aerosols is described in the prior art for disinsection, in particular, the use of fumigation bombs (see, for example, RU 2095983) and thermal sublimation devices (fumigators, see, for example, EP 1547464) vaporizing the active substance ( pesticide and / or repellent), which then, when condensed in air, forms a highly dispersed aerosol that is active against insects, since such an aerosol can enter the respiratory system, precipitate on the surface of the wings of flying insects, and when edanii at mucosal surface active substance readily diffuses deep into the body, because the fine particles dissolve rapidly.

Thus, based on the unique properties of quaternary ammonium bases, in particular didecyldimethylammonium halide, the attractiveness of the aerosol disinfection and disinsection method, the idea arose to implement a processing method (disinfection and / or disinsection) based on highly dispersed aerosols with a high content of active substance.

However, to implement this method, there are a number of objective obstacles.

It is known from the prior art that didecyldimethylammonium halide or its clathrate exhibits its properties as a disinfectant and / or disinsectant in solution (in a liquid medium) and when using additional components, such as alcohols, ketones, aldehydes, acids and oxidizing agents.

In this regard, it is quite natural that the composition proposed in the application RU

2004 104015, involves the use of a solution of didecyldimethylammonium clathrate urea halide, provided that an acid component in the form of an aerosol of non-drying particles with a size of at least 20 microns is included in this solution. This application can be considered as a prototype in relation to the present invention.

But with all the attractiveness of the use of disinfectants / disinfectants in aerosol form, there were no reports of the possibility of creating condensation aerosols of surfactants, in particular didecyldimethylammonium halide or its urea clathrate, which would exhibit the required types of activity.

Therefore, the present invention is directed to the creation of means and methods for aerosol disinfection / disinsection using didecyldimethylammonium halide or its clathrate as an active substance, where the active substance is used in the form of a highly dispersed condensation aerosol in the form of solid particles.

SUMMARY OF THE INVENTION

The present invention provides disinfection and / or disinfection means based on pyrotechnic compositions which contain a quaternary ammonium compound, such as didecyldimethylammonium halide, as an active ingredient. In particular embodiments, the substance used in pyrotechnic compositions is didecyldimethylammonium clathrate urea halide, where the halide is bromide or chloride. At the same time, pyrotechnic compositions suggest the combined presence of the active substance and the thermal composition in them, which ensure the combustion (smoldering) process and the sublimation of the active substance.

The compositions of the present invention are intended for disinfection and / or disinfection of objects. In this case, disinfection involves the destruction or inactivation of microorganisms related to viruses, bacteria and fungi, including influenza virus, avian influenza virus, hepatitis virus, HIV virus and parainfluenza virus, mycobacteria, bacteria and anthrax spores, staphylococci, Escherichia coli, Candida fungi dermatophytes. The composition, when applied, ensures the death of insects, including flying insects, and their larvae.

Objects subject to disinfection and / or disinfection can be any objects requiring disinfection / disinsection that can be processed in the gas phase. In particular, it should be especially noted that the objects of disinfection / disinsection are agricultural products or raw materials for food or feed products, finished food products or animal feed, as well as animals or poultry.

The invention provides a method for disinfecting and / or disinfecting premises, closed volumes, objects in an open area or in closed volumes by burning said pyrotechnic compositions containing didecyldimethylammonium halide or didecyldimethylammonium clathrate with urea as an active substance, and the effect of the obtained aerosol of the active substance on the processed for a time sufficient to achieve the required level of decontamination.

Due to the low toxicity of the active substance in warm-blooded (maximum permissible concentration of the working area for didecyldimethylammonium chloride - 1 mg per cubic meter), disinfection / disinsection can be carried out in the presence of animals or birds. This also involves the use of the means and methods of the present invention in the field of veterinary medicine, in particular for the treatment and prevention of diseases of animals and birds by destroying pathogen carriers, as well as pathogens themselves located on the skin, feathers, mucous membrane of the upper respiratory tract, etc. areas that are affected by pathogens and which are accessible for penetration and action of a highly dispersed aerosol of the active substance.

EFFECT: invention makes it possible to fully realize the known biocidal action of didecyldimethylammonium halide with respect to gram-positive and gram-negative microorganisms, including tuberculosis, pathogenic microorganisms of groups I and II, including causative agents of tuberculosis, salmonella, typhoid fever, dysentery, diphtheria, scarlet fever, venereal disease, venereal disease especially dangerous infections (plague, cholera, glanders, melioidosis, tularemia and anthrax), dermatophytes, yeast-like fungi of the genus Candida, as well as in relation to research institutes of viruses (viruses of hepatitis B, C, HIV, hepatitis A, herpes, influenza, parainfluenza). The present invention has been shown to be effective against pathogens of bacterial and fungal infections of potato, cattle infectious rhinotracheitis virus (RTI), causative agent of cattle viral diarrhea (VD cattle), cattle parainfluenza-3 virus (cattle flu-3), as well as unidentified viruses that are the causative agents of acute rhinovirus infections of cattle.

Based on the results obtained, the present invention is applicable in agriculture, in the food industry, in trade, in medicine, in veterinary medicine, in the household sector, in transport, as well as for the elimination of foci of infection and disinfestation in open areas.

The present invention is based on the unexpected discovery that, during the combustion of the pyrocomposition, the didecyldimethylammonium halide or didecyldimethylammonium halide clathrate with urea is melted and sublimated, followed by aerosol condensation. The removal of aerosol particles from the combustion zone (decay) occurs due to gaseous products of combustion, after which a condensation aerosol with unique properties is formed. The uniqueness of the properties of the obtained aerosol is due, on the one hand, to the small particle size (corresponding to the size of the aerosol smoke particles), as well as to the fact that these particles actively absorb moisture and combustion products of the pyro-composition. Thus, the obtained particles, in addition to the didecyldimethylammonium halide, contain moisture absorbed or adsorbed and pyrocomposition products of combustion. Moisture provides the formation of a reaction medium for the active substance, after it is deposited on the surface (object) subjected to disinfection / disinsection, and the combustion products are additional compounds that activate the active substance, providing a high level of activity of didecyldimethylammonium halide.

The combustion scheme of the pyrocomposition is shown in the drawing.

In the drawing, the numbers indicate: 1 - pyrotechnic composition; 2 - heating zone; 3 - region of the K phase; 4 - combustion surface; 5 - zone of atmospheric air; 6 - absorption zone of atmospheric water vapor and combustion products on the surface of the aerosol particle; 7 - a zone of formation of primary aerosol particles; 8 - high temperature zone.

During the combustion of pyrocomposition 1, there is a heating zone 2 and a region of K-phase 3, in which the formation of the gaseous phase of the active substance begins. The bulk of the vapor of the aerosol former is obtained in the high-temperature zone 8, directly adjacent to the region of the K phase. The atmospheric air 5 entering the stream of combustion products reduces its temperature, and as a result of condensation of the gaseous aerosol former in zone 7, primary aerosol particles are formed. The primary particles are carried by the stream to zone 6, where the absorption of gaseous products of combustion and atmospheric water vapor on the surface of the aerosol particle begins. Small smoke particles are characterized by high absorption of moisture from the environment. In this case, the partial pressure of water vapor above the particle surface becomes equilibrium with the surrounding air. A moistened aerosol particle is a solid substance of complex composition, but, nevertheless, it cannot be considered as a drop of solution.

Thus, it is clear that the resulting aerosol particle contains in certain proportions

(i) the active substance and

(ii) thermal composition combustion products, both in the form of (a) a solid (non-combustible residue), (b) condensate (combustion products, which under normal conditions are liquid), and (c) absorbed / adsorbed gaseous products of combustion.

The resulting fine particulate aerosol is distributed in the environment according to the laws of gas diffusion. In open areas - according to the laws of turbulent diffusion.

As the aerosol spreads, its particles settle on the surfaces due to gravitational forces, due to inertial forces, electrostatic interaction, Van der Waals forces, thermal diffusion forces, etc. At the same time, it is characteristic of highly dispersed aerosol particles that for a short period of time (for the first or second hour of aerosol life in volumes where there is no forced air movement), the concentration of deposited particles on horizontal surfaces (both above and below) and vertical surfaces approximately the same level. This phenomenon causes a high degree of penetration of fine aerosols.

Highly dispersed precipitated particles are characterized by a high degree of adhesion to the surface. As you know, the degree of adhesion is higher, the smaller the particle. In addition, the degree of adhesion is positively affected by the hydration layer formed on the surface of the didecyldimethylammonium halide particles due to the absorbed air moisture. Moreover, a settled particle without additional application of energy in one form or another cannot break away from the surface with which it is in contact.

Thus, if there is a contaminant on the surfaces of the object accessible to the aerosol, finely dispersed particles will come into direct contact with the spread of the aerosol and its exposure.

Any "living" environment, especially microorganisms, are characterized by a certain degree of water content. The degree of water content is the amount of free moisture that is not chemically bound in relation to the total water content (as a chemical compound) in a microorganism or other object. Live active microorganisms (i.e. excluding spores) are characterized by a water content of about 0.8. Thus, the microorganism itself or other living tissue can be a source of moisture for chemical reactions when it comes in contact with particles of solid (i.e., dry) substances.

It is probably this phenomenon that occurs when particles of solid disinfectants and living microorganisms come into contact. A regularity was noticed that the smaller the size of the solid particles of disinfectants, the higher their disinfecting ability based on weight. A similar observation was made with respect to pest control.

It is assumed that surfactants exhibit their activity against biological objects due to interaction with the lipid bilayer of cell membranes, either by including surfactant molecules in the hydrocarbon region of the bilayer, or by adsorption of these molecules in the zone of polar membrane phospholipids, or by incorporating surfactant molecules into both non-polar and and in the polar part of the membrane. This mechanism explains well the activity of surfactants against viruses, bacteria and fungi, as well as activity against spores of microorganisms, due to the blocking of the mechanism of transition of spores to the vegetative phase.

Surfactants as insecticides act on insects in a complex manner, killing insects in contact with almost any part of the body of the insect, disrupting the functioning of the tissue in contact with the surfactant, and then the entire organ associated with this tissue. Surfactants also act as intestinal poisons that penetrate the body of an insect through the organs of nutrition and kill it as a result of disruption of digestion and assimilation of food.

In addition, there is evidence that surfactant pairs can act as repellents.

Without going into the theoretical justification of the causes and bioactivity mechanism of surfactants, in particular quaternary ammonium bases, including urea halide didecyldimethylammonium clathrate, it should be noted that the phenomenon of inactivating action on microorganisms and insects takes place, and it can serve as one or another explanation of the patterns discovered by the authors, which formed the basis of the present invention.

Another aspect of the aerosol formation process according to the invention, resulting from the aerosol particle formation mechanism, is that combustion products are formed in addition to condensing vapors of the active substance during the combustion of the pyrosol composition.

The products of combustion reactions are characterized by the presence of highly active substances in them, including products of incomplete oxidative thermal conversion, and free radicals. Combustion products of organic substances include gaseous products such as carbon dioxide, water, nitrogen oxides, sulfur compounds, etc., as well as aerosol particles, which include soot (carbon particles), ash (inorganic substances) and resinous substances of complex and indefinite composition. It is noted that during combustion of products of plant origin, combustion products contain free radicals of the type (RO •), (R •) and (NO •) (see, for example, WO 2002/032239). These radicals are formed during the burning of almost any organic substance. Moreover, with a decrease in the combustion temperature, i.e. when the "smoldering" mode takes place, the amount of products of incomplete combustion increases. Resinous substances formed, for example, during the combustion of wood, include phenols, acids and carbonyl compounds (aldehydes, ketones). Liquid condensate of wood combustion products (liquid smoke) is used in the food industry for the manufacture of smoked meats and as a flavoring additive. This product is safe for use, and its composition and properties are regulated by technical conditions, for example TU 9199-002-55482687-02.

The studies of the applicants found that the addition of liquid smoke to the solution of didecyldimethylammonium halide clathrate with urea increased its biocidal activity.

The following premise, which is implemented in the present invention, was that the analysis of the products of combustion of almost all of the investigated substances traditionally used in the composition of thermosetting mixtures showed the presence of at least one of the following products: acid products, nitrogen oxides, phosphorus oxides, oxides sulfur, and in some cases, in direct experiments, the presence of free radicals was confirmed.

In this regard, experiments were proved in which the additional introduction of gaseous products of combustion to the vapors (aerosol) of didecyldimethylammonium halide increased the disinfectant activity of the active substance.

The studied thermo-sublimation mixtures belonged to chlorate-ammonia-anthracene compounds, chlorate-anthracene compounds, metal-chloride compounds (including chlorinated organic compounds as fuel), phosphorus-organic compounds, milk sugar and oxidizing agent compositions, smoky and smokeless powders, compositions based on sawdust, cellulose, peat chips, etc.

Typically, a heat-sublimation mixture includes fuel (e.g., anthracene, naphthalene, cellulose, coal, etc.) and an oxidizing agent (e.g., Bertholeta salt, nitrate, permanganate, etc.) as separate substances. The choice of specific components of binary mixtures, as a rule, is based on the preferences of developers and customers, since theoretically the selection of components and their quantitative ratios do not constitute any problems.

In some cases, the fulfillment of both functions, both fuel and oxidizing agent, is carried out by one substance, for example, in the case of nitrocellulose, the basis of smokeless powders.

The above components (or component) provide the combustion process (smoldering) and, as a consequence, the formation of thermocondensation aerosol of the active substance when it is added to the heat-sublimation mixture.

In addition to these components, the composition of the heat-sublimation mixture includes auxiliary components, for example, phlegmatizers, flame arresters, inert fillers, disintegrants, combustion stabilizers, and technological additives: binders, plasticizers, lubricants, water-repellent substances, etc. These auxiliary components, their choice in a particular situation, the amounts introduced into the composition, the form of administration and technological methods are known to specialists in this field.

For example, the introduction of an excess of ammonia into the heat-distillation mixture lowers the combustion temperature. In addition, ammonia forms sublimation centers during sublimation, on which another active substance condenses.

The compositions of thermo-sublimation mixtures and the principles of their construction are described in detail in the available literature of the prior art, see, for example, A. Freiman Short course of pyrotechnics. Oboronpromgiz, 1940, 148 p .; Bystrov I. A short course of pyrotechnics. Moscow, Artillery Academy of the Red Army, 1939, 223 pp .; Weizer Yu.I., Luchinsky G.P. Masking smoke. M .: Goskhimizdat, 1947, 202 p .; Shidlovsky A.A., Fundamentals of pyrotechnics. M .: Engineering, 1973, 320 p .; Chuvurin A.V. Entertaining pyrotechnics. In 2 hours - Kharkov: Osnova, 2003, 360 and 364 p.

In addition to traditional auxiliary components, the composition of thermo-sublimation mixtures may include inert fillers in the form of volumetric bodies, which perform the functions of a combustion stabilizer, a heat receiver, and a heat transfer body. For example, RU 2124839 discloses, as an additive, stabilizing the rate of combustion of a heat-sublimation mixture and providing heat transfer to an evaporating active substance, the use of ordinary silica sand or silica particles of 3-5 mm in size.

In the above literature, the principles of designing products for thermal sublimation of substances with predetermined parameters associated with the thermal stability of the sublimated substance are disclosed. In addition, the principles of product design are described there, in order to provide the desired burning rates.

Thus, constructive solutions in the field of formulation of thermal compositions and manufacturing of products are known from the prior art and understandable for specialists.

A distinctive feature of the pyrotechnic composition of the present invention is that it contains didecyldimethylammonium halide as an active substance. This substance may be included in the composition in the form of didecyldimethylammonium chloride or bromide or in the form of a mixture thereof. The active substance can be included in the composition in the form of a didecyldimethylammonium halide clathrate with urea.

The active (active) substance is introduced into the composition in an amount of from 7 to 30% by weight based on didecyldimethylammonium halide. The use of smaller amounts of the active substance is not economically feasible, and large quantities, as it turned out during the experiments, require the use of special techniques for the construction of thermal mixtures due to sintering of the mass during its burning (decay) due to melting of didecyldimethylammonium halide or didecyldimethylammonium clathrate with urea. The melting point of didecyldimethylammonium bromide clathrate with urea is about 145 ° C. The use of didecyldimethylammonium halide or didecyldimethylammonium halide clathrate with urea in the indicated amounts makes it possible to use typical compositions of thermal mixtures and traditional technologies for manufacturing products for the formation of fumes, since they allow sublimation of compounds with a specified melting point.

In addition, other agents that allow thermal distillation may be added to the composition of the invention, in addition to the active substance. For example, it is known to use a number of organic aromatic oils in thermal distillation mixtures (see WO 97/42814), which provide a repellent effect and also serve as flavoring agents. Such oils include fir oil, lavender oil, clove oil, cedar oil, lemon oil, etc., as well as their synthetic analogues. In order to increase insecticidal activity, other pesticides, for example, belonging to the pyrethroid series, may be additionally included in the composition (see WO 2005/082877). Antifungal agents may also be added (see, for example, WO 2005/074684). To increase the total effect with respect to fungi, sulfur can be included in the composition, which is easily sublimated, forming a highly active fungicidal aerosol (RU 2 042 658). In addition, metal chloride chloride-distillation mixtures can contain not only chloroparaffin, but also hexachlorane, which interacts with metallic aluminum and / or magnesium in the presence of zinc oxide, forming highly dispersed smoke containing both the products of the combustion of the chloro-organic compound and its condensation aerosol particles . In this case, hexachloran exhibits its insecticidal and repellent properties.

The presence of the above additional components in the aerosol, at least, expands the spectrum of activity of the composition, although in some cases a synergistic effect is possible. The basic requirement for additional components is not to react with didecyldimethylammonium halide. However, this requirement is easily fulfilled in practice due to the fact that the didecyldimethylammonium halide does not apply to highly reactive substances.

The traditional technology for the manufacture of pyrotechnic products (devices) involves the mixing of wet or dry components, molding the product by pressing, thermal pressing, extrusion, etc. and, if necessary, drying, impregnating with additional components or applying a protective coating. The molded mixture may optionally be placed in a housing (shell) made of non-combustible or combustible material, or pressing may be carried out immediately in the specified shell. In the case of a combustible shell, for reasons of fire safety, it is advisable to use a fireproof bottom in the product. When forming the product, if necessary, channels can be made in it, facilitating the combustion process and the exit of products. The need to use the channels is due to the composition of the thermal mixture and the requirements for its burning rate. In particular, there is a pattern between the burning rate and the degree of porosity of the pressed product: a larger number of channels leads to a higher burning rate. Thus, the burning rate of the composition can be controlled by the composition of its components, manufacturing technology and geometry of the finished product.

The finished product (device) can be made in the form of a cylinder, briquette, pyramid, rod, spiral, etc.

To be protected from external factors and to harden the surface of the product, it can optionally be coated with a protective composition, for example, a layer of drying oil or drying oil, varnish, including shellac, nitro-varnishes, an adhesive coating, for example, a solution of starch, carboxymethyl cellulose, etc.

Examples of cylindrical products include traditional smoke bombs or candles. Spirals are used in household burnable repellent / insecticidal devices. An example of a fumigant helix design is disclosed in WO 97/42814.

If necessary, the product may include a firing element or igniter, which may be integral with the resulting pyrosostructure or attached to it as a component. An example of a separate igniter is an ignition match or a heat cord. Alternatively, a primer layer is applied to the top of the molded pyrotechnic mixture, consisting, for example, of a mixture of bertholite salt, phosphorus, iron oxide and a binder.

The resulting pyrotechnic products have been comprehensively tested, provided for by the norms and safety rules for handling smoke compositions and pyrocompositions. Since standard formulations of thermal compositions and product designs were used, in this case, additional tests and safety certifications were not required. The operation of such products is possible by ordinary personnel, as well as in domestic conditions, without suggesting special measures for the training and qualification testing of personnel.

The use of developed pyrocompositions or products containing pyrocomposition for disinfection and disinsection involves burning the pyrocomposition in the confined space where the processed object is located, or burning the pyrocomposition (or using the product containing the specified pyrocomposition) in an open area, so that the processed object is in a smoke plume, which is easy to visualize. The burning of the composition according to the invention or the use of an article containing the composition is carried out on the windward side of an object located in an open area. When applied on the ground, the amount of composition burned is determined on the basis of known dependencies that take into account the removal of an object, weather conditions, etc., so that the desired effect is achieved as a result of aerosol exposure

After exposure to an aerosol resulting from the combustion of a pyro-compound, an object is not necessarily aired for a predetermined time (exposure time). These operations are the essence of the method of disinfection and / or disinfection of contaminated objects. In addition to the specified method, the developed pyrocomposition provides protection of objects from damage by microorganisms or insects for a long time, since the deposited particles of the active substance are firmly held on the surface of the treated object, and the active substance, being in a "dry" state, is resistant to external factors, with the exception of flushing with liquids in which it dissolves. Thus, the creation of a layer of particles of the active substance on the surface of the object protects the object from subsequent exposure to contaminants.

The features of the active substance used, such as didecyldimethylammonium halide, ensure the implementation of all its previously identified activities against microorganisms, and also ensures the achievement of a pesticidal and, in part, repellent effect. The types of activity of the active substance are described and proved in detail in a number of publications of the prior art, in particular, see patents RU 2095086, RU 2158141, RU 2221424, RU 2214837 and EA 000113, as well as application RU 2004 104015.

In addition, the present invention has proven to be useful in veterinary practice. Due to the fact that the generated aerosol has a particle size equivalent to the “aspirable” fraction, like any smoke and thermocondensation aerosol, it easily penetrates the respiratory organs of animals, where it destroys pathogens. In addition, due to the good adhesion of particles to the skin of animals, hair or feathers, the active substance effectively acts against pathogens and / or insects parasitizing on animals or birds, and also provides a long-lasting protective effect from subsequent contamination.

When evaluating the effectiveness of the composition according to the invention, it was found that the active substance used in the form of a condensation aerosol was effective for the destruction of ectoparasites in chickens. Directly after exposure to didecyldimethylammonium halide aerosol on chickens, a significant decrease in the number of ectoparasites (ticks, lice-eaters) was established. The chickens from the group treated, after they were transferred to the general house, showed a lower level of ectoparasite damage with their repeated control after 3-5 days. This showed the presence of a cumulative effect of the active substance, which suggests the possibility of using the invention to prevent bird damage.

Unexpectedly, the positive effect of the obtained aerosols was found in the treatment of not only infectious diseases of animals caused by pathogens, but also as an adjunct in the treatment of inflammatory diseases of the skin of unclear etiology, with injuries and damage to the skin, with neurogenic dermatoses, etc., since the use of aerosol of solid particles of didecyldimethylammonium halide excluded at least secondary infection of skin lesions in animals and birds during the acute stage of the disease .

In general, disinfection ensures the inactivation of microorganisms related to viruses, bacteria and fungi. Examples of viruses are influenza virus, bird flu virus, hepatitis virus, HIV virus, parainfluenza virus, cattle rhinotracheitis virus, cattle diarrhea virus and the like. Examples of bacteria are mycobacteria, bacteria and anthrax spores, staphylococci, salmonella, E. coli, streptococci. Examples of fungi are Candida, dermatophytes, fungi that cause damage to plants, in particular potatoes, etc. A list of pathogens that are effectively affected by the didecyldimethylammonium halide is known in the art. The present invention discloses and proves that the biocidal action of the didecyldimethylammonium halide is biocidal when used in the form of a thermocondensation aerosol.

The composition according to the invention has low toxicity to warm-blooded. In this regard, its use is possible by personnel having the simplest means of protection at the time of use. Post-exposure operations do not require respiratory protection.

The burning time of the product containing the composition of the present invention varies from 1 minute to 30 minutes. This duration is determined by the processing requirements. Small volumes may allow rapid combustion of the mixture. In large volumes, characterized by low air velocities, prolonged combustion is advisable, while filling the volume more uniformly. Regulation of the duration of combustion is carried out by varying the composition and / or form of the product. For example, compact products with a high degree of compaction and in the presence of additional channels (expanded combustion area) burn faster than the same cylinders (candles, spirals) without channels and with a lower degree of compaction during pressing. Some compositions, for example, based on wood dust or peat, are characterized by a low burning rate, in contrast to a chlorate-ammonia-anthracene mixture or a mixture based on milk sugar and an oxidizing agent.

Thus, the present invention implements the previously identified activity of the active substance and provides new technical effects associated with the possibility of aerosol treatment, according to its characteristics and advantages, corresponding to gas treatment (low consumption of active substance, high penetrating ability of particles, ease of use, no labor-intensive removal of disinfectant / disinfectant residues from treated surfaces, etc.); provides a device that combines in its composition both the active substance and the means providing the application; expands the arsenal of disinfection and pest control; offers a new method of disinfection and disinsection with a thermo-condensing aerosol of didecyldimethylammonium halide.

Based on the results obtained, it is quite obvious the use of the composition according to the invention for the protection of food, fodder, textiles, etc. objects that may be biodeteriorated during storage. The ability of an aerosol to fill volumes, its low toxicity to warm-blooded animals, including humans, the ability to cumulative effect and the persistence of the most active (active) substance of a composition involves the use of an aerosol to protect objects from biodeterioration. Biological damage refers to damage to an object by microorganisms or insects during their life, valuable objects or products. Moreover, even assuming a low activity of the aerosol against spores, the didecyldimethylammonium halide will fulfill its biocidal functions when the spore transitions to the vegetative stage. Since the damaging effect is possible only by active forms of microorganisms, the didecyldimethylammonium halide deposited on the surface of the protected object will fulfill its biocidal properties when the spore transitions to the active phase or directly affects the microorganism in its active form or on the pest insect. It is obvious that such treatments can be carried out repeatedly in order to reduce a single acting dose of the active substance or as necessary.

The technical result of the present invention is achieved by reducing the size of aerosol particles, obtaining these particles in a solid, essentially anhydrous form, incorporating thermomixes in the composition of the particles, which have an activating effect on didecyldimethylammonium halide, increasing the penetration of the particles of the active substance and its adhesion, which associated with particle size reduction.

The present invention is further illustrated by examples showing embodiments of the invention, as well as proving the achievement of the claimed results.

Examples

Materials and methods

To prove the activating effect of combustion products on didecyldimethylammonium halide, experiments were carried out using "liquid smoke" (TU 9199-002-55482687-02). Qualitative experiments were carried out using solutions and aerosols, in which it was proved that "liquid smoke", applied in amounts from 0.5 to 20% by weight of the active substance, significantly increases the activity of the active substance - didecyldimethylammonium halide, in particular didecyldimethylammonium bromide clathrate with urea.

In addition, in studies of the condensation aerosols of didecyldimethylammonium halide obtained by thermal sublimation in an electric heater in the presence of combustion products of a number of thermal compositions (wood dust; wood dust + fir oil; nitrocellulose; chlorate-ammonia-anthracene mixture; metal-chloride composition, composition based on and bertoletovoy salt), which were also introduced into the aerosol chamber, where the test objects were located, an increase in the activity of the active substance compared with the control, when test objects exposed to an aerosol of didecyldimethylammonium halide.

Bioactivity experiments were conducted with test microorganisms. Pest control studies have been conducted using flies and mosquitoes.

For a quantitative assessment of the disinfecting ability of the aerosol and preliminary testing of the disinfection regimes, standard test objects were used, which were batista strips that were impregnated with a suspension of test microorganisms and then dried. For example, if an anthrax causative agent, B. anthracis (STI strain), is used as a test culture, the strips are impregnated at the rate of 0.5 ml of a suspension of microorganisms with a concentration of approximately 2 × 10 ⁹ cells / ml per 1 test object. This microorganism is extremely stable and can exist both in the vegetative and spore form.

In addition, cups with a dense medium, on which a test culture was applied, were used as test objects for studies. Such test systems made it possible to evaluate the effect of disinfecting aerosol on microorganisms immediately after sowing on a dense medium or after preliminary incubation, when the colonies were already visualized.

However, based on the requirements of modeling the conditions of contamination, the most visual and evidence-based are test objects in the form of solid substrates coated with a suspension of microorganisms with a protective substance. For example, in a number of experiments, wooden substrates contaminated with Staphylococcus aureus (strain 209-P) and coated with a tread - horse serum at a rate of 1 ml per 100 square meters were used. see the surface of the test object.

When using viral cultures, they were applied to wooden and concrete test substrates in the presence of a tread - cattle serum.

After aerosol exposure, flushes were performed from the test objects and analyzed by traditional methods. Cup test objects were incubated after exposure and colony counts were performed.

In addition, direct experiments were conducted on the effects of the didecyldimethylammonium halide aerosol obtained by burning the composition of the invention on real objects, such as samples of stored potatoes.

Studies were conducted on the disinfection of vivarium premises with the control of indicative microflora.

Also, experiments were conducted on the disinfection of the premises of calf houses and poultry houses in the presence and absence of animals (birds).

The revealed possibility of aerosol treatment in the presence of animals made it possible to carry out a series of experiments on the use of a didecyldimethylammonium halide aerosol obtained by burning the composition of the invention for therapeutic purposes with monitoring the condition of animals affected by viral diseases. In addition, the presence of ectoparasites in animals (birds) was monitored before and after treatment.

For research, compositions were used, which were pyro-compounds containing a heat-sublimating mixture and an active substance (didecyldimethylammonium halide).

Laboratory (chamber) experiments were carried out using product models, which are 12 gauge sleeves filled with the test composition. If necessary, channel systems were formed in the models to change combustion modes. To set the mixture on fire, termite matches were used or, alternatively, an igniter composition was applied to the top of the model.

In some cases, model products were pressed in the form of a rod with a diameter of 8 mm and a length of 40-80 mm.

Model products were used for testing in aerosol chambers.

For experiments in rooms or in large-volume chambers, model products were used, which were cylindrical briquettes with a total mass of approximately 50, 100, and 200 g or a set of rods assembled in a shell, so that the assembly had channels between the rods.

The particle size of the aerosol formed during the combustion of the pyrotechnic composition was controlled using cascade impactors. During the experiments, it was found that the maximum mass average particle size (D _max ) never exceeded 10 μm, and the average median particle size of the aerosol (D ₅₀ ) in all cases was less than 4 μm. Particles having a size of more than 5-10 microns were aggregates.

During laboratory experiments during the development of disinfection regimes, the concentration of the active substance was determined by standard methods, for example, titration in the presence of sodium lauryl sulfate. Samples were taken in liquid bubblers (impingers) or filters, followed by extraction of the analyte. In some cases, impactors were included in front of the samplers, which provided cut-off of particles with a size of more than 10-15 microns. Samplers with nozzles were used mainly in field and field conditions, when the air contained a large number of particles with a size of more than 10-15 microns, which practically did not contain the active substance, with the exception of part of the particles deposited on coarse aerosol particles.

During field tests, premises for storing food products, in particular, potato storage facilities, laboratory vivariums, calf houses, and poultry houses were subjected to aerosol treatment.

For testing on the basis of the available information, various formulations of thermo-sublimation mixtures were selected. Based on them, pyrocompositions were prepared by introducing didecyldimethylammonium halide or didecyldimethylammonium clathrate of urea halide into them.

The compositions were prepared, as a rule, by sequential mixing of the components, moistening the mixture, pressing and drying.

The compositions, from the point of view of the technology for producing pyrotechnic compositions, allowed the inclusion of the active substance in amounts of up to 90% by weight due to its good wettability and compressibility. The ratio of the components was selected experimentally, using the laws of the design of mixtures known from the prior art.

In some cases, the active substance acted as a component of the fuel, which, when melted and burned, absorbed excess heat. In this regard, it was recognized that the conversion factor of the active substance to aerosol cannot be the main criterion for choosing the composition of the composition. Nevertheless, preference was given to those formulations that provided a high transfer of the active substance into the aerosol phase.

Examples of pyrocomponents containing didecyldimethylammonium halide (in some cases in the form of a didecyldimethylammonium halide clathrate with urea) as active ingredient (DV), which were obtained for experimental verification, are given below. The indicated ranges of the component contents reflect the ranges of their changes during the preparation of the samples that were tested. Samples were prepared so that it was possible to evaluate the boundary values of the indicated intervals and 1-3 values within the interval.

1. Compositions based on wood dust and cellulose fibers:

1a . wood dust (particle size less than 0.5 mm) - 40-80%,

oxidizing agent (KNO ₃ ) - 5-10%,

DV (urea didecyldimethylammonium clathrate) -5-50%.

1b . wood dust (particle size less than 0.5 mm) - 50-80%,

fir oil - 5-10%,

DV (urea didecyldimethylammonium clathrate) -5-50%.

1s wood dust (particle size less than 0.5 mm) - 40-80%,

turpentine - 5-7%,

DV (urea didecyldimethylammonium clathrate) -15-50%.

1d . wood dust (particle size less than 0.5 mm) - 40-80%,

turpentine - 5-7%,

colloidal sulfur - 10%

DV (urea didecyldimethylammonium clathrate) -15-50%.

1e . fibrous cellulose - 55-90%,

KNO ₃ - 1-5%,

DV (urea didecyldimethylammonium clathrate) -5-30%.

1f. fibrous cellulose - 55-90%,

KNO ₃ - 1-5%,

nitrocellulose - 1-5%,

DV (urea didecyldimethylammonium clathrate) -5-30%.

1g. fibrous cellulose - 40-70%,

KNO ₃ - 1-5%,

nitrocellulose - 1-5%,

NH ₄ Cl - 10-20%

DV (urea didecyldimethylammonium clathrate) -5-30%.

1h . wood dust (particle size less than 0.5 mm) - 60-80%,

oxidizing agent (KNO ₃ ) - 10-20%,

DV (didecyldimethylammonium bromide) - 10-30%.

1i . wood dust (particle size less than 0.5 mm) - 60-80%,

oxidizing agent (KNO ₃ ) - 15-20%,

DV (didecyldimethylammonium chloride) - 5-20%.

1k . wood dust (particle size less than 0.5 mm) - 70%,

fir oil - 10%,

DW (didecyldimethylammonium bromide) - 20%.

2. Compositions based on peat chips:

2a . peat chips (particle size less than 2 mm) - 50-80%,

oxidizing agent (KNO ₃ ) - 3-10%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-40%.

2b . peat crumb (particle size - less than 2 mm) - 50-90%,

turpentine - 5-7%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-50%.

2s peat chips (particle size less than 2 mm) - 50-80%,

turpentine - 5-7%,

permethrin - 0.5-2%

DV (didecyldimethylammonium bromide clathrate with urea) - 5-50%.

2d . peat crumb (particle size less than 2 mm) - 70%,

turpentine - 5%,

DV (didecyldimethylammonium bromide) - 25%.

3. Compositions based on nitrocellulose

3a. nitrocellulose - 40-60%,

filler (sand, gypsum, particle size 0.5-2 mm) - 20-30%

NH ₄ Cl - 10-40%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-30%.

3b. nitrocellulose - 10-20%,

fibrous cellulose - 10-15%,

NH ₄ Cl - 5-20%,

filler (gypsum, powder) - 5-20%,

4. Powder based compositions

smoke powder - 10-30%,

NH ₄ Cl - 5-40%,

filler-binder (gypsum, cement) - 5-20%,

DV (urea didecyldimethylammonium clathrate) - 15-70%.

5. Formulations based on milk sugar

5a. milk sugar - 20-25%,

KClO ₃ - 15-35%,

NH ₄ Cl - 5-30%,

sand (particle size 1-2 mm) - 0-10%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-70%.

5b. milk sugar - 20-25%,

KClO ₃ - 20-25%,

sodium bicarbonate - 5-15%,

talc - 5-20%,

DV (didecyldimethylammonium bromide clathrate with urea) - 10-60%.

6. Anthracene-based formulations

6a. anthracene - 12-45%,

KClO ₃ - 10-45%,

NH ₄ Cl - 0-30%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-45%.

6b. anthracene - 12-45%,

KClO ₃ - 10-45%,

wood dust (particle size less than 0.5 mm) - 5-50%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-45%.

6 sec DV (didecyldimethylammonium bromide clathrate with urea) - 5-45% thermal composition (55-95% of the total weight of the composition)

anthracene - 7-17%,

KClO ₃ - 40-50%,

NH ₄ Cl - 40-50%.

7. Compositions based on organochlorine compounds

7a. chloroparaffin - 30-60%,

Al / Mg mixture powder - 3-15%,

zinc oxide powder - 5-25%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-45%.

7b. hexachloran - 30-60%,

Al / Mg mixture powder - 3-15%,

zinc oxide powder - 5-25%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-50%.

7a. chloroparaffin - 20-50%,

Al / Mg mixture powder - 3-10%,

zinc oxide powder - 5-20%,

gypsum, talc (1: 1 mixture) - 5-20%,

DV (didecyldimethylammonium bromide clathrate with urea) - 5-45%.

8. Compositions based on red phosphorus

red phosphorus - 5-10%,

KNO ₃ - 15-30%,

NH ₄ Cl - 10-40%,

talc - 5-20%

DV (didecyldimethylammonium bromide clathrate with urea) - 5-70%.

9. Compositions based on pyrocomposition and smoke mixtures produced by industry

In known compositions for fumigation and disinsection, part or all of the active substance (indicated in the recipe) was replaced with didecyldimethylammonium halide.

9a. Composition based on the registration of the smoke bomb G-17 (TU 84-22-76), having the original composition:

technical hexachloran - 50%

Bertoletova salt - 25%

ammonium chloride - 10%

technical anthracene -10%

dicyandiamide - 5%

In this composition, both part and the entire amount of hexachlorane was replaced by didecyldimethylammonium bromide or didecyldimethylammonium clathrate with urea.

9b. Composition based on the registration of smoke bombs D-20 and D-18, having the original composition:

DDT technical - 50%

Bertoletova salt - 25%

ammonium chloride - 14%

anthracene - 6%

dicyandiamide - 5%

In this composition, both part and the entire amount of hexachlorane was replaced by didecyldimethylammonium bromide or didecyldimethylammonium clathrate with urea.

The resulting compositions were subjected to pyrotechnic tests, during which the following results were established.

By selecting the content of the components, it is possible to control the burning rate of the mixture and its effective temperature.

Compositions containing more than 50% didecyldimethylammonium halide or didecyldimethylammonium clathrate urea halide have unstable combustion characteristics, and in some cases tend to self-extinguish.

The introduction of ammonium chloride or inert fillers reduces the combustion temperature of the mixture.

By molding the mixture into products of various shapes, it is possible to control the burning rate of the products and, therefore, to some extent the combustion temperature.

The use of didecyldimethylammonium halide in the form of a urea clathrate is more technologically advanced for wet pressing operations, which makes it possible to obtain uniformly burning compositions by direct compression of a mixture of wet components.

Research in an aerosol chamber showed that the tested compositions, which are characterized by a lower combustion temperature, provide a greater transfer of the active substance into the aerosol phase.

When burned, all the compounds provided for the conversion of didecyldimethylammonium halide to an aerosol form, which was easily determined organoleptically by a specific odor. In addition, in necessary cases, objective control of the presence of the active substance in the aerosol was carried out by sampling and analysis.

Mixtures having a “zero” or negative balance with respect to the oxidizing agent (that is, its lack in terms of stoichiometric ratios) provide the best translation of the active substance into the aerosol state.

The obtained results of pyrotechnic tests do not contradict the information of the prior art in the field of smoke formation and sublimation of organic compounds by combustion (decay) of pyrocompositions.

When conducting chamber tests, it was found that all the compounds generate a didecyldimethylammonium halide aerosol, although the coefficient of conversion to aerosol state varied widely. However, this indicator was not criterial, since the technical result of the present invention is the creation of a highly dispersed condensation aerosol of didecyldimethylammonium halide against the background of thermal composition combustion products.

Assessment of biological activity.

To prove the activating effect of combustion products on didecyldimethylammonium halide, experiments were carried out using "liquid smoke" (TU 9199-002-55482687-02). Qualitative experiments were carried out using a 0.1% solution of didecyldimethylammonium bromide clathrate with urea, to which an additional 0.01% liquid smoke concentrate was added.

The tested microorganisms are Escherichia coli, Staphylococcus aureus and fungi of the Candida genus.

As a result, the synergistic effect of liquid smoke on the activity of didecyldimethylammonium bromide clathrate with urea was qualitatively established.

Varying the concentration of liquid smoke in the range from 0.5 to 20% by weight of the active substance did not show a pronounced quantitative effect on the increase in the activity of the active substance. Thus, the activating effect of wood combustion products on the activity of didecyldimethylammonium halide with urea was proved.

The next series of experiments was carried out using liquid samples of the products of combustion of thermal compositions and solutions of didecyldimethylammonium halide clathrate with urea.

Samples of thermal compositions that did not contain didecyldimethylammonium halide were burned and samples were taken into liquid bubblers from the aerosol chamber.

Samples from bubblers were combined with a solution of didecyldimethylammonium bromide clathrate with urea, based on the predicted ratio of the active substance (didecyldimethylammonium halide) and a thermal composition of 1: 4.

Qualitative experiments were carried out using staphylococci and anthrax spores as test microorganisms.

For vegetative bacteria, a concentration of 0.1% for the active substance was used, and for spores - 3%.

It has been established (at a qualitative level) that the products of combustion of all pyrocomponents activate the disinfecting effect of a solution of didecyldimethylammonium bromide clathrate with urea.

The next series of experiments was aimed at establishing the activating effect of the combustion products of pyrocompositions on the aerosol of didecyldimethylammonium halide.

For this, a condensation aerosol of didecyldimethylammonium clathrate urea clathrate, obtained by thermal sublimation in an electric heater, was introduced into the aerosol chamber through the nozzle. Thermal composition combustion products were simultaneously introduced into the aerosol chamber through another nozzle. The ratio of the mass of the sublimated sample of the active substance (didecyldimethylammonium halide) to the mass of the burnt sample of the thermal composition was approximately 1: 4.

Batiste strips soaked in a culture of microorganisms and dried before being placed in the chamber were used as test objects. The strips were placed under the caps that protected them from direct aerosol sedimentation.

After exposure, flushing was carried out from the strips, which was subjected to biological analysis. Strips not exposed to the aerosol, as well as strips exposed to the aerosol of only didecyldimethylammonium halide, were used as control.

The exposure time of the test strips in the chamber was 30 minutes in the case of vegetative forms of bacteria, 3 hours for spore forms. The exposure time and aerosol concentration were chosen so as to exclude complete deactivation of the samples to ensure the reliability of the data obtained.

The results of the analysis showed that the products of combustion of thermal compositions activate the disinfecting effect of the aerosol of didecyldimethylammonium halide.

The effect of combustion products of the following thermal compositions was investigated:

wood dust + nitrate (10: 1);

wood dust + fir oil (10: 1);

peat crumb + turpentine (10: 1);

nitrocellulose + ammonia (2: 1), with the addition of phlegmatizers;

milk sugar + bertoletova salt (1: 1), with the addition of phlegmatizers;

red phosphorus + nitrate + ammonia (1: 3: 2), with the addition of phlegmatizers;

the composition of the D-20 checkers (without DDT).

In all cases, an increase in the activity of the active substance was established compared with the control when the test objects were exposed to aerosol of only one bromide or didecyldimethylammonium halide clathrate with urea.

Thus, the conducted experiments prove that the didecyldimethylammonium halide has a disinfecting activity when it is found in the form of a highly dispersed aerosol obtained by the thermal condensation method.

Based on the experiments, specific prescriptions for thermal compositions were selected, which were used for further tests to evaluate the effectiveness of disinfection / disinsection.

On the basis of the selected thermal compositions, pyro-compositions were prepared, i.e. compositions according to the invention, by incorporating the active substance into the heat-sublimating mixture.

As a model, the formulation was selected with the following components: KClO ₃ - 45 ± 5%, NH ₄ Cl - 45 ± 5%, C ₁₄ H ₁₀ (anthracene) - 12 ± 5% (chlorate-ammonia-anthracene mixture). Urea in the amount of 5, 10, 15, 20, 25, and 30% based on the total weight of the formulation was introduced into this mixture didecyldimethylammonium clathrate with urea.

In another series of experiments, didecyldimethylammonium bromide was used as the active substance, which was introduced into the initial formulation of the specified composition in amounts of 25 and 30% based on the total weight of the formulation.

We also investigated a formulation containing wood dust and fir oil in a ratio of 10: 1, into which 10, 20, and 30% didecyldimethylammonium bromide clathrate with urea was added, based on the total weight of the formulation.

For model products based on a chlorate-ammonia-anthracene mixture in the form of a cylinder with a diameter of 18 mm and a length of 60 mm, a sample burning rate of approximately 0.4 mm / s was obtained. Thus, a model product weighing about 20 g burned out in 4 minutes. Model products based on wood dust, pressed in the form of a rod with a diameter of 8 mm, had a burning rate of about 0.1 mm / s, which ensured longer burning of the samples.

The amount of didecyldimethyl ammonium bromide or didecyldimethyl ammonium bromide clathrate with urea introduced, within the tested ranges, had practically no effect on the burning rate.

These samples when tested in an aerosol chamber showed the transfer of the active substance into the aerosol phase at a level approximately equal to 30-85%. The highest values of aerosol transfer occurred when lower amounts of the active substance in the formulation were used.

Biological tests carried out in chamber conditions using test objects allowed to prove the effectiveness of the method against bacteria (vegetative and spore forms), fungi, viruses and to determine indicative disinfection modes.

As test objects, batiste strips, wooden substrates, ceramic substrates with microorganism suspensions applied to them, as well as cups with culture seeds were used.

On wooden and ceramic test objects, solutions were applied containing cultures and a tread, which, as a rule, was serum. Test objects were placed on the ceiling, walls and floor of the chamber (room).

In addition, concentrations were determined at which model animals and birds could be in the volume subjected to aerosol treatment.

The effectiveness of the composition against flying insects (flies, mosquitoes) was also evaluated.

General patterns were established during disinfection, on the basis of which recommendations were developed for optimizing treatment regimes in the premises.

In particular, the effectiveness of disinfection increases with increasing humidity and temperature in the rooms. However, it was found that disinfection can be carried out at low temperatures. In this case, the exposure time or concentration of the active substance in the aerosol must be increased.

As a result of direct experimental estimates, it was found that the optimal consumption rate of the composition (for the active substance) is 0.2-0.4 g per cubic meter, under normal climatic conditions. This concentration is carried by animals (birds), but, on the other hand, it causes the death of pathogenic microorganisms.

In particular, quantitative indicators of insemination by staphylococci and salmonella at an exposure of 30 minutes are reduced by 2 times. E. coli is completely destroyed. After 24 hours of exposure, salmonella was completely inactivated (complete absence in samples). Staphylococcus level decreased by 4 times.

It should be noted that after daily exposure, the tested microorganisms showed growth retardation compared to the control. The growth inhibition was about 24 hours, which indicates the bacteriostatic effect of the aerosol, in addition to the revealed direct bactericidal action.

The aerosol concentration, equal to 0.3 grams of active substance per cubic meter, made it possible to completely destroy flies and mosquitoes in the volume of the chamber (room).

By increasing the concentration of aerosol, the exposure time can be reduced. When the composition was consumed at the rate of 25 g of active ingredient per 40 cubic meters, complete inactivation of staphylococcus and Escherichia coli was established on test objects containing a protective substance.

In addition, with such a consumption rate (about 0.6 g / m ³ ) during the disinfection of the vivarium premises, with an exposure time of 3 hours, no sanitary microorganisms were found in the control washes from the surfaces and equipment.

During the disinfection of the premises of livestock complexes (i.e., in the absence of complete sealing, but with the ventilation turned off), it was established that with a consumption rate of 0.3 g / m ³ (for the active substance), the inactivation of infectious rhinotracheitis viruses, infectious diarrhea and cattle parainfluenza-3 with an exposure of 60 minutes. In this case, animals can be in the treated room.

With periodic processing of the premises where young cattle are kept, with a frequency of 3 times a week according to the above regimen, a favorable effect on animals was noted in acute respiratory diseases.

When processing rooms where animals with a genital form of infectious rhinotracheitis of cattle were kept, a significant decrease in the duration of the clinical manifestations of the disease and their severity was noted.

Processing of houses with a consumption rate of 0.3 g / m ³ (according to the active substance) and an exposure time of 60 min ensures partial inactivation of controlled microflora and complete destruction of flying insects. Pecking by a bird of dead insects did not lead to any pathological deviations from the gastrointestinal tract. By periodically processing the premises of the houses, it was possible to significantly reduce the level of contamination of surfaces and equipment for controlled microorganisms.

The increase in exposure time led to a significant decrease in the number of ectoparasites on the body of birds during a controlled period. The level of traumatic skin lesions in the bird also decreased.

When monitoring the treated chickens, it was found that in the treated group there was a more rapid healing of traumatic injuries of the skin.

A group of chickens, rejected due to the presence of damage to the skin, complicated by infection, was subjected to aerosol treatment (mode - 0.3 g / m ³ , exposure 1 hour). The level of surviving chickens on the second or third day was significantly higher than in the control.

The results obtained prove the effectiveness of the developed composition for disinfection / disinsection in the presence or absence of animals (birds), as well as for their treatment.

Another series of experiments confirmed the effectiveness of the application of the developed composition for biocidal processing of potatoes stored for storage.

Traditional processing involves uniformly spraying potato tubers with a solution of biocide, and then additional drying. The use of aerosol treatment with the drug and the method according to the invention provides for the treatment of tubers without pouring and mixing, which eliminates mechanical damage to the tubers on conveyors, and also does not require drying after processing.

Processing was carried out on seed potatoes of the Detskoselsky variety.

Controlled types of rot during storage:

Phytophthora infestans (late blight),

Erwinia carotovora (bacterial soft or black leg rot),

Rhizoctonia solani (rhizoctonia),

Phoma solanicola (dry rot, or phomosis).

Processing was subjected to potatoes at the rate of 20 g of active substance per ton of tubers.

Compared with the control in the test batch, these types of rot were completely absent. Control (without treatment) - 2% of tubers are affected. Fungicidal treatment ensured the safety of potatoes for 6 months.

Another experiment on the treatment of seed potato tubers was carried out with Agria, which had an initial level of damage of 15%.

Controlled types of potato rot:

Phytophthora infestans (late blight),

Erwima carotovora (bacterial soft or black leg rot),

Streptomyces scabies (common scab),

Rhizoctonia solani (rhizoctonia),

Phoma solanicola (phomosis),

Clavibacter michigonensis sub. sp. sepedonicum (ring rot),

Fusarium solani (Fusarium, or dry rot).

Storage temperature 1-5 ° C, consumption rate of 20 g of active substance per ton of tubers.

The total incidence of seed was 13%; of them fungal nature: late blight (1.5%), fusarium (2.5%); phomosis (4.0%); bacterial etiology: 1.5% (wet rot); 1.0% (ring rot), as well as actinomycetes, (2.0%) the causative agent of common scab.

The test results indicate that the test composition showed fungicidal activity against rot during storage of potatoes (a decrease in the level of damage compared to control):

28-40% (late blight);

40-50% (fusarium);

31.0-66.7% (phomosis);

53.5-56.6% (wet bacterial rot);

40.0-48.6% (ring rot).

The period of the protective action of the fungicide: up to 6 months.

The phytotoxic effect of the composition on tubers was not observed during the entire period of storage of potatoes.

Thus, the developed composition provided effective protection of potatoes against the development of fungal and bacterial lesions. It should be noted that in the latter case, the processing was carried out at a low temperature, when the use of traditional drugs by the irrigation method is difficult.

The above data and examples prove the industrial applicability of the present invention and disclose it in detail in the form of preferred embodiments. These examples are not restrictive.

Claims (38)

1. Pyrotechnic composition for creating an aerosol of didecyldimethylammonium halide containing
as the active substance, didecyldimethylammonium halide or its urea clathrate;
thermal composition, which during combustion provides the sublimation of the active substance. 2. The composition according to claim 1, used for disinfection and / or disinfection. 3. The composition according to claim 2, where the disinfection includes the destruction or inactivation of microorganisms related to viruses, bacteria and fungi. 4. The composition according to claim 3, where the disinfection provides inactivation of viruses, such as influenza virus, bird flu virus, hepatitis virus, HIV virus, parainfluenza virus. 5. The composition according to claim 3, where the disinfection provides the inactivation of bacteria, such as mycobacteria, bacteria and anthrax spores, staphylococcus, E. coli. 6. The composition according to claim 3, where the disinfection provides the inactivation of fungi of the genus Candida, dermatophytes, fungi that cause damage to plants. 7. The composition according to claim 2, where pest control ensures the death of flying insects and their larvae. 8. The composition according to claim 2, where the pest control ensures the death of ectoparasites of animals or birds. 9. The composition according to claim 2, where the disinfection and / or disinsection is carried out in the presence of animals, birds and / or people. 10. The composition according to claim 2, where the disinfection and / or disinfection of agricultural products or raw materials for food or feed products, finished foods or animal feed. 11. The composition according to claim 1, intended for the treatment of traumatic injuries of the skin of animals or birds. 12. The composition according to claim 11, where skin lesions are complicated by infection. 13. The composition according to claim 1, where the content of the active substance is from 7 to 30% by weight. 14. The composition according to claim 1, where the active substance is a didecyldimethylammonium bromide clathrate with urea. 15. The composition according to claim 1, where the active substance is a didecyldimethylammonium chloride clathrate with urea. 16. The composition according to claim 1, where the thermal composition is a chlorate-ammonia-anthracene mixture. 17. The composition according to 14, where the thermal composition consists of NH ₄ Cl in an amount of from 40 to 50%, KClO ₃ in an amount of from 40 to 50%, C ₁₄ H ₁₀ (anthracene) in an amount of from 7 to 17%. 18. The composition according to claim 1, where the thermal composition is nitrocellulose or smoke powder. 19. The composition according to claim 1, where the thermal composition is a mixture of wood dust and inorganic salt from the number of perchlorates and nitrates. 20. The composition according to claim 1, where the thermal composition is a mixture of wood dust and fir oil. 21. The composition according to claim 1, where the composition further comprises an inert filler (fillers), to reduce the temperature of combustion, reduce the rate of combustion and phlegmatization of combustion of the thermal composition. 22. The composition according to item 21, where powdered metal oxides, gypsum powder, ground talc, cement, sand, or mixtures thereof are used as filler. 23. The composition according to claim 1, compressed in the form of a volumetric body. 24. The composition according to item 23, where the volumetric body has internal channels. 25. The composition according to item 22 or 23, containing a coating selected from among the drying oils and / or polymers. 26. The composition according to item 22, which has an additional device for ignition. 27. A smoke generating pyrotechnic product for disinfection and / or disinsection, containing the composition according to any one of claims 1 to 26. 28. The product according to item 27, containing a combustible shell and a fireproof bottom. 29. The product according to item 27, made in the form of a cylinder. 30. The product according to item 27, equipped with an ignition device for igniting the composition. 31. The product according to item 27, having a burning time of from 1 to 30 minutes 32. A method of disinfecting and / or disinfecting objects, comprising burning a composition according to any one of claims 1 to 26 or using the product according to any one of claims 27 to 31 as an aerosol source of the active substance. 33. The method according to p. 32, performed in closed volumes. 34. The method according to p, performed in an open area. 35. The method according to clause 34, where the source of aerosol of the active substance is located on the windward side of an object located in an open area. 36. A method of protecting objects from agricultural products, food, feed and textile products from biodeterioration during storage, comprising burning the composition according to any one of claims 1 to 26 or using the product according to any one of claims 27 to 31 as an aerosol source of the active substance in closed volumes where the processed objects are located. 37. The method according to clause 36, performed repeatedly during the storage period of the processed objects. 38. A method of exterminating insects parasitizing on the skin and hair of animals and on the skin and feathers of a bird, comprising burning a composition according to any one of claims 1 to 26 or using the product according to any one of claims 27 to 31 as an aerosol source of the active substance, and exposure animals or birds for a time sufficient to kill parasitic insects.