RU2599004C1 - Emulsion formulation for disinfection of surfaces - Google Patents

Abstract

FIELD: hygiene.

SUBSTANCE: invention relates to disinfecting and degassing of surfaces and can be used at elimination of consequences of emergency situations, technogenic accidents or terrorist acts using toxic substances and biological pathogenic agents. Emulsion bifunctional formula of oxidative-nucleophilic action for disinfecting and degassing surfaces contains aqueous hydrogen peroxide, isopropyl alcohol and chlorobenzene or dichloroethane in the following ratio of components (vol%): hydrogen peroxide - 10; isopropyl alcohol - 54; chlorobenzene or dichloroethane - 17; water - the rest. To increase disinfectant properties of the formula at temperatures lower than minus 15 °C is additionally added 1.0 % (volume) of formic acid.

EFFECT: invention provides effective disinfection and decontamination of surfaces contaminated toxic organophosphorus substances and pathogenic microorganisms in temperature range from minus 30 to 40 °C during no more than 60 minutes, at that the shelf life of the finished formulation is not less than 3 years without changing its properties.

1 cl, 7 tbl, 2 ex

Description

The invention relates to multifunctional formulations for the disinfection and degassing of various surfaces infected with vegetative and spore forms of microorganisms, as well as toxic organophosphorus substances, including under conditions of negative (up to minus 30 ° C) temperatures. The invention can be used in the elimination of the consequences of the use of chemical and biological weapons, as well as the consequences of emergencies, industrial accidents or terrorist acts with the use of toxic substances and biological pathogenic agents. In addition, the invention can be used to ensure the safety of work in chemically and biologically hazardous facilities.

State of the art

To eliminate the consequences of the use of toxic substances (OM) and biological weapons (BW), time-based formulations are used that have a degassing and disinfecting effect based on chlorine-containing preparations (aqueous solutions or suspensions of calcium hypochlorites, formulations using chloramines, dichloro and trichloroisocyanuric acid compounds). For degassing and disinfection of objects infected with vegetative forms of microorganisms, 1.0-1.5% aqueous solutions of calcium hypochlorites are used; 5.0-7.5% aqueous solutions are used in the treatment of objects infected with spore forms of microbes. Among the main disadvantages of formulations based on calcium hypochlorites include a high specific consumption (1.5-4.5 l · m ^-2 ), a narrow temperature range of use (5 ° C and above), low efficiency against toxic substances, due to weak extracting ability of aqueous formulations, short shelf life of finished suspensions (from 2 to 5 days) [1, 2].

For degassing, polydegassing solvent formulations of RD and RD-2 nucleophilic action are used. Polydegassing formulations of RD and RD-2 provide effective disinfection of objects from organic matter in a wide temperature range (from minus 60 to plus 40) with a small flow rate of 0.4-0.5 l · m ^-2 , have a long shelf life of 5 years, but do not have disinfectant activity. In addition, the aforementioned chlorine-containing and solvent formulations have a strong destructive effect on structural materials (especially paints and varnishes) of the processed objects [1, 2].

Various oxidizing formulations have also been developed for the neutralization of toxic chemicals and pathogenic biological agents, including compounds containing xenon difluoride 0.5-1.0% [3], active oxygen in the form of hydrogen peroxide, inorganic and organic compounds as an oxidizing component peroxide compounds in an amount of from 2.0 to 25.0% [4-6] and various functional additives.

The degassing and disinfecting effectiveness of these formulations, as well as their consumption per unit of the treated surface (exposure time from 1 to 6 hours, flow rate from 0.2-0.5 to 1.0 l · m ^-2 ) [3-6] are comparable to personnel recipes [1, 2, 7, 8]. The disadvantages of these bifunctional formulations include a large number (from 5 to 13) of the components that make up the composition. Functional additives reduce the aggressive effect on the processed materials, expand the possibilities of application (in the form of foam or aerosol, thickened compositions are better held on inclined surfaces). But at the same time, the process of preparing recipes is complicated (it becomes multi-stage) and lengthens up to 1 hour, and in patents [4, 6] - up to 3-6 hours or more, the shelf life of ready-made recipes is short and ranges from several hours to a day. Certain recipes cannot be stored in finished form due to the rapid loss of activity of the target components [3, 4], they are prepared immediately before use.

The patents [3-6] indicate that the products of the interaction of thickened formulations with OM or microorganisms are low toxic and do not pose a danger to humans. However, the composition of the formulations themselves includes components related to toxic substances of hazard class 2 and 3 (hydrogen peroxide with a concentration of 35.0-50.0% and peroxide compounds, alkalis, xenon difluoride, acetonitrile, fatty alcohols, quaternary ammonium compounds, hydrochloric acid ) After application, the thickened compositions, as well as service degassing and disinfecting compositions, leave a film, plaque or dried foam on the treated surface, with which short-term contact is allowed (10-15 minutes) without skin protection. However, for the subsequent long-term safe operation of objects from their surface, it is necessary to remove the remnants of formulations, or use skin protection products.

The closest analogues to the present invention are hydrogen peroxide solutions recommended by the sanitary and epidemiological rules of SP 1.3.1285-03 [7] for the disinfection of various objects contaminated by pathogenic microorganisms: 3.0% (from bacteria), 6.0 and 10.0 % (from spores, viruses, chlamydia, rickettsiae and fungi) with the addition of 0.1-0.5% surfactants and (or) 1.0% formic acid, at low temperatures additionally add up to 40% isopropyl or ethyl alcohol [7, 9].

The solutions have high disinfecting properties (depending on the type of surface and microorganism, the exposure is from 60 to 120 minutes, the flow rate during irrigation processing is from 0.3 to 0.9 l · m ^-2 ). However, their drawback is the low extraction ability common to all aqueous formulations, as a result of which they provide only surface degassing of objects.

In this regard, the development of a single highly effective formulation for degassing and disinfection is an urgent task.

The aim of the present invention is to develop an economical multifunctional formulation of oxidative nucleophilic action with improved performance characteristics, providing at low consumption in a wide temperature range, effective disinfection of surfaces contaminated with microorganisms, as well as toxic organophosphorus substances. Improving operational characteristics is to reduce the duration and simplify the procedure for preparing the recipe, to increase the shelf life of the finished recipe, as well as to reduce the destructive effect of the recipe on coatings.

The claimed technical result is achieved by the composition of the emulsion formulation, which contains an aqueous solution of hydrogen peroxide as an inorganic oxidizing agent, two organic solvents, one of which is aprotic non-polar, the second is protic polar, and formic acid with the following ratios of components, vol%:

hydrogen peroxide - 10;

chlorobenzene or dichloroethane - 17;

isopropyl alcohol - 54;

formic acid - 1 (added in the case of using the formulation at an ambient temperature below minus 15 ° C);

water is the rest.

Hydrogen peroxide interacts with OM molecules and structural elements of microorganisms, causes their oxidative destruction, as a result of which OM molecules turn into low-toxic compounds, and microorganisms lose their viability. Formic acid was used in the formulation as an activator to enhance the oxidizing effect of hydrogen peroxide at low ambient temperatures.

Chlorobenzene and dichloroethane are aprotic non-polar solvents that contribute to a good extraction of OM, absorbed into structural materials and coatings of treated objects, and also increase the rate of decomposition of toxic organophosphorus substances.

Isopropyl alcohol plays the role of a nucleophilic agent in the inactivation of OM, antifreeze, which allows the formulation to be used in winter conditions (up to minus 30 ° С), as well as an emulsifier when mixing polar and nonpolar liquids during the preparation of the formulation, resulting in the formation of a stable emulsion retains its effectiveness and state of aggregation without deterioration for at least three years.

Despite the fact that peroxide-containing compounds exist in solid form (hydroperite), the recipe used hydrogen peroxide in liquid form with a concentration of the main substance of at least 35%, which eliminates the stage of dissolution of solids and thereby simplify the technology and significantly reduce its preparation time. The components used are the products of large-tonnage productions of the domestic chemical industry, and are relatively inexpensive, which allows us to conclude that the claimed formulation is economical.

The essence of the invention is to obtain an emulsion formulation by mixing the components in the calculated quantities.

Knowing the volume of containers in which the emulsion formulation will be prepared, calculate the amount of each component individually, taking into account the composition (volume%) and the conditions of its use:

hydrogen peroxide (PV) - 10;

chlorobenzene (CB) or dichloroethane (DCE) - 17;

isopropyl alcohol (IPA) - 54;

formic acid (MK) - 1 (added in the case of using the formulation at an ambient temperature below minus 15 ° C);

water is the rest.

To prepare the emulsion formulation, technical grade B hydrogen peroxide is used with a basic substance content of at least 35% and the remaining components with a purity qualification no worse than technical ones.

The calculation of the amount of technical hydrogen peroxide for the preparation of the formulation is carried out according to the formula 1:

Where

V _PV - the amount of technical hydrogen peroxide needed to prepare the recipe, l;

10 - the content of hydrogen peroxide in the formulation,%;

With _PV - the content of hydrogen peroxide in the technical hydrogen peroxide,%;

V _ER - the volume of the formulation, l

Pour the calculated amount of technical hydrogen peroxide, chlorobenzene (or dichloroethane) and isopropyl alcohol into the container, if necessary, add formic acid, then mix thoroughly for 1-2 minutes. Pour the components into the container in any order. The finished formulation has the form of a transparent homogeneous liquid.

The recipe can be prepared immediately before use or in advance, the shelf life of the finished recipe is at least three years.

The recipe is used for its intended purpose by irrigation or irrigation with simultaneous wiping with brushes using modern special processing equipment equipped with stainless steel tanks (for example, KDA kit, USSO station, UTM-80M machine). It is possible to use recipes from technical means of special processing (for example, ARS filling stations of various modifications) equipped with a liquid intake system from an external source (for example, a high-capacity container made of high-pressure polyethylene) without using its own ferrous metal container.

It is forbidden to use emulsion formulations from special processing equipment having ferrous metal containers and not equipped with a fluid intake system from an external source, bypassing its container. It is forbidden to use emulsion formulations from technical means working using the energy of exhaust gases of the object being processed. In the process of applying the formulation for its intended purpose, it is necessary to use personal protective equipment for the skin and respiratory organs.

The recipe is used at temperatures from minus 30 to 40 ° C. The consumption of the formulation is 0.2-0.3 l · m ^-2 . The exposure during the disinfection of surfaces infected with microorganisms, including spores, is not more than 60 minutes, the exposure during degassing is not more than 60 minutes.

Upon completion of degassing and disinfection work, the surface of the treated objects is washed with water.

The possibility of implementing the claimed invention, the effectiveness of the formulation under various options and conditions of use, as well as the absence of the destructive effect of the formulation on the paint coatings are confirmed experimentally in laboratory conditions.

Example 1. The technology of preparation of the recipe, operational characteristics

The amount of each component of the formulation was calculated separately, taking into account the composition (volume%) and the conditions of its use (table 1). The amount of hydrogen peroxide of technical grade B was calculated according to formula 1, taking into account the content of the main substance in it of 35.0% (according to laboratory control data using a permanganometric volumetric method).

When preparing 10 l, the calculated amount of components was poured into the container, then thoroughly mixed with a mixer (plastic bar) manually for 1 minute. The total cooking time (taking into account the measurement of all components) was no more than 5 minutes.

When preparing the recipe in the container of the KDA kit, the pumping of the components from the factory packaging and their mixing was carried out using the special equipment included in the machine, in accordance with the instruction manual. The total cooking time was from 20 to 30 minutes.

The crystallization temperature of the emulsion formulation was determined using an ATKt-02 apparatus (manufactured by Spetsneftekhimavtomatika LLC, Ufa), designed to determine the crystallization onset temperature of low-freezing liquids and antifreeze. The determination was carried out according to the method described in the instruction manual of the device.

As a result of the tests (table 2), it was found that the crystallization temperature of the emulsion formulation containing chlorobenzene is minus 37.0 ° C. The recipe containing dichloroethane begins to freeze at a temperature of minus 33.4 ° C. The addition of 1.0% formic acid reduces the crystallization temperature of the formulations by 1.0 ° C. Thus, at ambient temperatures up to minus 30.0 ° С the formulations will be guaranteed to be in a liquid state and can be used for surface treatment in winter conditions.

The effect of the emulsion formulation on the paint coatings was evaluated by the change in adhesion (the method of lattice notches according to GOST 15140-78) and the appearance of the coating (visually according to GOST 9.407-84) and the photoelectric method by the change in gloss (according to GOST 896-69). The tests were carried out in laboratory conditions using metal test objects, painted with XB-518 paint. The formulations were applied by irrigation and brush irrigation with a flow rate of 0.3 l · m ^-2 and an exposure of 60 minutes, after which the test objects were washed with water and dried. Processing was carried out five times.

It was experimentally established (Table 3) that the fivefold effect of the tested formulations practically does not affect the properties of the paint coating: adhesion does not change, the appearance does not change when visually determined, the gloss of the coating worsens slightly (not more than 6.0%).

Example 2. The effectiveness of the formulation

The formulations were prepared in accordance with the described technology. The tests were carried out at positive and negative values of the ambient temperature in the range from minus 30.0 to 40.0 ° C.

The degassing effectiveness of the formulations was evaluated in the laboratory using test surfaces made of various materials infected with a model Vx type poisonous substance with a density of (1.0 ± 0.1) mg · cm ^-2 . After infection, the surfaces were treated with an emulsion formulation by irrigation or brushing irrigation. After the formulation was dried (depending on the experimental conditions, the drying process takes from several minutes to 1 hour), sorbent polymer substrates were applied on the surface, using which the residual content of model OM was determined by biochemical control. The test results are presented in table 4.

The experimental data presented in table 4 show that effective degassing of all surfaces is achieved in no more than 60 minutes when they are processed with a flow rate of 0.2 l · m ^-2 at positive ambient temperatures. In the case of surface degassing at air temperatures below 0 ° C, it is necessary to increase the flow rate to 0.3 l · m ^-2 .

The disinfecting effectiveness of the formulations was evaluated under natural conditions using samples of military equipment and insulating skin protection agents and in laboratory conditions using test surfaces made of appropriate materials (glass, painted metal, protective fabric with a polymer coating). The tests used formulations freshly prepared and stored for three years. For contamination of the surfaces, B.anthracis agar spore culture (vaccine strain STI-1) with mature spore content of at least 90% was used.

Bacteriological samples were taken from surfaces using a flush method using cotton-gauze swabs. The determination of the number of microorganisms in bacteriological samples was carried out by the cup method in accordance with Guide Ρ 4.2.2643-10 “Methods of laboratory research and testing of medical prophylactic disinfectants to assess their effectiveness and safety”. The tests were carried out in triplicate, the completeness of neutralization of the residual effect of the emulsion formulation in bacteriological samples was not less than 70%, the results are presented in tables 5-7.

The experimental data presented in tables 5 and 6 show that surface treatment with an emulsion formulation with a flow rate of 0.2 l · m ² ensures their effective disinfection from spores of microorganisms in 5 minutes in the temperature range from 15 to 40 ° C. When disinfecting surfaces in the temperature range from minus 30 to 15 ° C, complete disinfection is achieved in 60 minutes. At ambient temperatures below minus 15 ° C, to increase the disinfecting properties, it is necessary to add 1% formic acid to the formulation. The test results presented in table 7 indicate that the disinfecting properties of the emulsion formulation after three years of storage have not changed.

Since the claimed emulsion formulation provides for the complete destruction of B.anthracis spores (anthrax, vaccine strain STI-1), which are one of the most resistant forms of microorganisms, under experimental conditions, it also applies to other less stable microorganisms (bacteria, viruses, fungi, etc. .) It will also be effective.

Thus, the claimed emulsion formulation is bifunctional, it provides effective degassing and disinfection of surfaces infected with toxic organophosphorus substances and (or) vegetative and spore forms of microorganisms in a wide temperature range (from minus 30 to 40 ° C) for a period of not more than 60 minutes. The consumption of the formulation is 0.2-0.3 l · m ^-2 .

The recipe can be used by irrigation or irrigation with simultaneous wiping with brushes using modern special processing equipment equipped with stainless steel tanks (KDA kit, USSS station, UTM-80M machine) or equipped with a liquid intake system from an external source (ARS of various modifications). The recipe can be prepared immediately before use or in advance, the shelf life of the finished recipe is at least 3 years without changing its properties.

In comparison with the presented analogues, the emulsion formulation has improved operational characteristics: simplified cooking technology; cooking time is reduced to 30 minutes (in tankers) and up to 5 minutes - in small (up to 10 l) volumes; the destructive effect of the formulation on coatings is negligible or absent.

INFORMATION SOURCES

1. Guide to special processing. - M .: Military Publishing, 1988. (Chapter 2).

2. V.L. Rud. Special processing of troops // Textbook in three parts. Part 1. Substances, preparations and formulations. - M.: Publishing House of the Military Academy of Chemical Protection, 1988. (Chapters 4 and 6).

3. Bifunctional oxidation-nucleophilic formulation. Patent 2099115 RU, IPC ⁶ A62D 3/00 / Aleinikov N.N. (RU), Biryukova N.E. (RU), Burtovoy S.P. (RU), Kashtanov S.A. (RU), Kirillova T.M. (RU), Masalitina E.S. (RU), Menzelenko CB (RU), Nikiforov G.E. (RU), Rud V.L. (RU), Shadrin L.N. (RU); Applicant and patent holder Military Academy of Chemical Protection (RU); declared 01/17/1995; publ. 12/20/1997.

4. Composition for neutralizing chemical and biological toxic agents. Patent 2241509 RU, IPC7 A62D 3/00, B01F 17/18, B01F 17/38, C11D 1/62, C11D 3/39 / TEDROS MAYER E. (US), TUKER MARK D. (US); Applicant and Patent Holder SANDIA CORPORATION (US); declared 12/08/2000; publ. 12/10/2004.

5. Gel-forming formulation of oxidizing and nucleophilic action for the neutralization of surfaces. Patent 2351380 RU, IPC A62D 3/38 (2007.01), A62D 3/36 (2007.01), A62D 101/00 (2007.01) / Polyakov V.S. (RU), Gorshkov A.P. (RU), Mikhailov B.I. (RU), Malekin S.I. (RU), Ermilov V.V. (RU), A. Leshenevsky (RU); applicant and patent holder Scientific Research Institute of Elastomeric Materials and Products Limited Liability Company (NIIEMI LLC) (RU); declared 12/28/2007; publ. 04/10/2009.

6. Bifunctional oxidation-nucleophilic formulation. Patent 2248234 RU, IPC ⁷ A62D 3/00 / V. Kholstov (RU), Orlov V.N. (RU), Kuchinsky E.V. (RU), Anoshin CB (RU), Grigoryev V.P. (RU), Buyanov V.V. (RU), Nikolskaya V.P. (RU), Menzelenko CB (RU), Karpov V.P. (RU) Silaev V.G. (RU), Kravchenko I.I. (RU); applicant and patent holder Federal State Unitary Enterprise “State Research Institute of Biological Instrumentation” (FSUE “GosNII BP”) (RU), Military Unit 52688 (RU), MAPO-FOND OJSC (RU); declared 04/08/2003; publ. 03/20/2005.

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Claims (2)

1. Emulsion bifunctional oxidation-nucleophilic formulation for disinfection and degassing of surfaces, containing an aqueous solution of hydrogen peroxide and two organic solvents, characterized in that one of the solvents is isopropyl alcohol, and the second organic solvent is chlorobenzene or dichloroethane with the following ratios of components (volumetric %):
hydrogen peroxide - 10;
isopropyl alcohol - 54;
chlorobenzene or dichloroethane - 17;
water is the rest. 2. Emulsion bifunctional oxidation-nucleophilic formulation according to claim 1, characterized in that at temperatures below minus 15 ° C it additionally contains 1.0% (volume) of formic acid.