RU2634448C1 - Liquid composition of irritating action for self-defense means (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: composition is used as a throwable mass for a special-purpose cartridge, in particular, in aerosol small-size type canisters BAM and BAMP used in the barreled shooting devices for metered aerosol sprays such as "UDAR", or pyro-liquid (pyromechanical) cartridges used in the devices "OSA", "Strazhnic". The liquid irritating composition for self-defense means comprises, at least, one irritant, a thickener, dimethylsulfoxide and an organic solvent or a mixture of organic solvents, which contains glycerol triacetate or a mixture of glycerol tri-, di- and monoacetates with glycerin triacetate content of, at least, 54 wt % with the appropriate ratio of components. The version of the liquid composition is characterized by the absence of dimethylsulfoxide. Additionally, the liquid formulation may contain a colourant.

EFFECT: increasing the effectiveness of the irritating fluid, both in terms of the degree of impact and the range of throwing, while maintaining the formulation before it hits the target.

4 cl, 1 tbl, 10 ex

Description

The invention relates to means of self-defense of the population, in particular to liquids with the irritating effect of non-lethal effects on humans, used as the missile mass of a cartridge for special purposes, in particular in small-sized aerosol cans BAM and BAMP, used in barrelless shooting devices for metered-dose aerosol spraying "BLOW", or pyro-liquid (pyromechanical) cartridges used in devices "OSA", "Guard".

Variants of the liquid composition of the irritant effect are known (RF Patent No. 2483051, IPC C06D 7/00, application. 01.10.2009, publ. 05.27.2013). In the known liquid composition, at least one irritant, at least one organic solvent mixed with a propellant is used. The composition contains dimethyl sulfoxide or dimethyl sulfoxide and a fat-alcohol-soluble dye, or dimethyl sulfoxide and water and a water-alcohol-soluble dye, and as a propellant - a liquefied gas or a mixture of liquefied gases with a boiling point above -45 ° C, or compressed gas with a boiling point below - 60 ° C. The technical result of the invention is to increase efficiency and reduce toxicity.

As a prototype, an irritating liquid composition for self-defense means was selected (RF Patent No. 2381205, IPC C06D 7/00, application form 14.07.2008, publ. 02.10.2010) containing at least one irritant, thickener, dimethyl sulfoxide and an organic solvent or a mixture of organic solvents in the following ratio, wt. %:

irritant 0.15 ÷ 4 organic solvent 23.5 ÷ 94.6 dimethyl sulfoxide 2 ÷ 35 thickener 1.4 ÷ 55

An organic solvent or a mixture of organic solvents can be: monohydric alcohol - ethyl or isopropyl, a mixture of 1,1,5-trihydrooctafluoroheptanol and 1,1,7-trihydrododecafluoroheptanol or propylene glycol. All of these solvents tend to evaporate during the flight of droplets when throwing an irritating liquid, causing a decrease in efficiency due to a decrease in the proportion of the substance delivered to the target and a decrease in the throwing range of the liquid formulation.

The objective of the invention was to increase the effectiveness of irritating liquids both in terms of exposure and range.

This problem is solved by options for the liquid composition of the irritating effect.

According to the first embodiment, the liquid irritant composition for self-defense means containing at least one irritant, thickener, dimethyl sulfoxide and an organic solvent or mixture of organic solvents, according to the proposal, it contains glycerol triacetate or a mixture of tri-, di- and monoacetates of glycerol as an organic solvent with a glycerol triacetate content of at least 54 wt. %, in the following ratio of components, wt. %:

irritant 0.5-6.0 glycerol triacetate or mixture glycerol tri-, di- and monoacetates 64-94 dimethyl sulfoxide 2-20 thickener 1-10

Dimethyl sulfoxide (DMSO) increases the quantitative characteristics of the results of using irritating formulations (see the description of the invention to the patent of the Russian Federation No. 2381205, prototype), but it has a slight drawback: during prolonged storage it partially decomposes, therefore, for example, in medical preparations where it yes, the shelf life is usually limited to two years. In the considered area of application - 3-4 years. In addition, in combination with DMSO, it is not advisable to use irritants with relatively high toxicity, such as CN (hazard class 1) and CS (hazard class 2), because exposure to such irritants may increase to an unacceptable level.

Accordingly, the irritant liquid composition according to the second embodiment does not contain DMSO, while in the same way as in the first embodiment, it contains glycerol triacetate or a mixture of glycerol tri-, di- and monoacetates with a content of glycerol triacetate of at least 54 wt. %, in the following ratio of components, wt. %:

irritant 1.0-6.0. glycerol triacetate or mixture glycerol tri-, di- and monoacetates 84-98 thickener 1-10

For both options, it is preferable to add dye in the composition in an amount of 0.001-0.1% wt. %

The proposed liquid composition of the annoying effect allows to obtain the following technical result.

1. An increase in efficiency due to the fact that a large proportion of the formulation, and hence the irritant contained in it, reaches the target. This is explained by the fact that flying (as a result of a shot) drops of an annoying formulation based on triacetin practically do not decrease in mass and therefore reach the target by 90%. The most likely reason is the very low vapor pressure of triacetin at temperatures up to 40-50 ° C. From the drops practically no evaporation occurs during the flight to the target. In previously known formulations, the main components of the solvent, comprising from 20 to 40% of the mass. % of the composition, under ordinary conditions, have a significant vapor pressure, which leads to their substantial evaporation during the flight of the droplets and, accordingly, a decrease in the mass of the droplets, because of which they do not reach the target.

2. An increase in the effective range of the shot with an annoying composition. Moreover, the range of the proposed formulation slightly exceeds the range of compositions based on fluorinated organic solvents, despite the fact that the latter have a higher density than triacetin (on average, 1.3 times). However, due to the much higher vapor pressure of fluorinated solvents (see table 1, nos. 7 and 8), there is a significant decrease in droplet mass during flight and, as a result, the effective throwing range of the triacetin-based formulation is greater.

3. Actually triacetin refers to food and cosmetic products. Accordingly, working conditions are improved in the manufacture of cartridges and cartridges. Used non-toxic irritating substances - “algogens” (literally - causing pain ”), which are in a solution of triacetin, also pose no danger (their vapor pressure is negligible). Irritating, and even more toxic, vapors are not observed even in the absence of exhaust ventilation.

In addition, the cost of producing an irritating composition is reduced, since triacetin is much cheaper than fluorinated solvents (the most affordable and cheapest of them are fluorinated alcohols, 7-9 times more expensive than triacetin).

It should also be noted that according to certain criteria, with respect to a solvent for irritating formulations, triacetin is similar to glycerin, which is also completely harmless and has the same very low vapor volatility at ordinary temperature. However, glycerin freezes easily. The melting point of glycerol is + 20 ° C, the melting point of triacetin is -78 ° C (table 1, No. p / p 1, 2). Triacetin is a unique substance that has both such a low freezing point and a high boiling point (260 ° C). A high boiling point causes very low vapor volatility at ordinary temperature. Liquid formulations based on glycerol and others (see, for example, RF patents No. 3 2157359, 2381205 (prototype)) give the necessary properties due to additives having significant volatility, for example, for the discussed problem, for example monohydric alcohols (isopropyl, ethyl and other).

In addition, glycerin is too viscous, and irritants are poorly soluble in it.

Thus, glycerol-based formulations always contain significant amounts of other solvents that eliminate these disadvantages, but tend to evaporate during the flight of droplets when throwing an irritating liquid, causing a decrease in efficiency due to a decrease in the proportion of the substance delivered to the target and a decrease in the throwing range of the liquid formulation.

In addition, in the environment of glycerol, as well as other polyhydric alcohols (ethylene glycol, propylene glycol), the irritant CN degrades (see, for example, the description of the invention to RF patent No. 2197456).

Mineral oils, in particular spindle oil (RF patent No. 2197456), which, according to a number of indicators, have a good combination of a number of physicochemical properties: very low vapor pressure at 20 ° C, low freezing temperature (table, 1, n / a 2), suitable viscosity. However, due to the relatively low density (0.87 g / cm ³ ), the throwing range of the formulation is relatively small. In addition, mineral oil is a hydrophobic solvent (completely insoluble in water). This is probably the reason for the weakening and "slowing down" of the action of the irritant on the moist mucous membranes of the eyes and respiratory tract (low efficiency). BAM with an irritant based on spindle oil (as well as other mineral oils) have not received distribution, despite the cheapness and availability of this oil product. Triacetin, unlike mineral oils, is a water-soluble substance.

The following table 1 shows the main physico-chemical characteristics of triacetin and a number of other solvents known from the prior art.

The vapor pressure values of the given substances at 20 ° C are taken from reference books, or calculated according to the Clausius-Clapeyron equation based on boiling points.

The vapor volatility at 20 ° C is largely consistent with vapor pressure at the same temperature, but is determined experimentally. Since volatility data at 20 ° С are not available for most of the substances listed, the table gives indirect (relative) data characterizing volatility — the mass loss of the substance during evaporation (in wt.%) From a fixed open tank in an active fume hood (last column of the table ) Data received by the applicant. All samples were in the same conditions.

Note to table 1

* The content of glycerol triacetate is not less than 54 wt. % (main impurities: glycerol diacetate and glycerol monoacetate).

Unlike food, technical triacetin can have a significant color and is used as a hardener of phenolic resins. To solve this problem, technical triacetin is suitable, containing: at least 54 wt. % glycerol triacetate; from 3 to 28 wt. % glycerol diacetate; from 1 to 14 wt. % glycerol monoacetate; no more than 4 wt. % glycerol and other impurities. Such technical triacetin in properties relevant to the claimed material is not inferior to food, containing, as a rule, at least 98 wt. % (up to 99.9 wt.%) glycerol triacetate, and irritating formulations based on it have excellent ballistic properties.

It should also be noted that the method for determining the loss of mass of a solvent during evaporation in a stream of flowing air at 20 ° C can only approximately reflect the fraction of the mass loss of a given substance from a missile mixture, when fired, a mixture in which this solvent usually makes up only part of the missile formulation . Perhaps that is why when throwing comparison formulations based on ethylene glycol and propylene glycol (table 1, items 5 and 7, thickener - glycerin), the mass fraction of the substance reaching the screen from a distance of 3 m is much smaller than for triacetin based formulations. While the weight loss of ethylene glycol and propylene glycol indicated in the table is relatively small (about 0.5 and 1 wt.%, Respectively). In the case of triacetin, mass loss, in the conditions of the experiment, is practically absent.

The following are examples of a liquid composition with one or two (mixtures) of active substances (irritants), various solvents and thickeners.

When describing the examples used the following abbreviations:

DMSO - dimethyl sulfoxide;

CR dibenz [b, f] -1, 4-oxazepine;

CS 2-chlorobenzylidene malonodinitrile;

IPC - pelargonic acid morpholide;

OS95 - oleoresin capsicum 95 (95% selective red pepper extract);

OS10 - oleoresin capsicum 10 (10% selective red pepper extract);

PVA - polyvinyl acetate well soluble in triacetin in granules;

TAC - cellulose triacetate;

PMMA - Dacryl brand polymethyl methacrylate (soluble in triacetin).

By the name "triacetin" is meant a food-grade product (food supplement E-1518) with a glycerol triacetate content of at least 98 wt. % Under the name "technical triacetin" - a non-food product containing at least 54 wt. % glycerol triacetate, from 3 to 28 wt. % glycerol diacetate, from 1 to 14 wt. % glycerol monoacetate and not more than 4 wt. % glycerol and other impurities.

The effective throwing distance was determined as the minimum distance of the UDAR firing device to the paper target, on which a spot with a diameter of 15-30 cm appeared, consisting of traces of colored drops, the maximum distance between which did not exceed 5-7 mm, which, among other things, provides guaranteed penetration of annoying recipes into the open eyes of the attacker.

1. Examples of formulations in the first embodiment (with DMSO)

Example 1.1

An irritating liquid composition containing commercial triacetin as a solvent (98 wt% of the main substance), irritant CR, a toughness enhancer - DMSO, a thickener - Dacryl 71 PMMA, a fat-soluble Sudan red G dye, in the following ratio components, mass. %:

Triacetin 94.0 CR 1,0 DMSO 2.0 Dacryl 71 2.99 Sudan Red G 0.01

The mass fraction of the composition that reached the target from a distance of 3 m is 88% (1.76 g out of 2.0 g).

The effective throwing range of BAM 60 (2 g of the formulation) is 6 m.

Example 1.2

According to example 1.1, characterized in that the solvent contains technical

triacetin (54 wt.% tri-, 28 wt.% di-, 14 wt.% glycerol monoacetate), pelargonic acid morpholide (MPC) was used as an irritant, and glycerin was used as a thickener, in the following ratio of components, wt. %:

Technical Triacetin (54% glycerol triacetate) 64.0 IPC 6.0 DMSO 19,99 Glycerin (thickener) 10.0 Sudan Red G 0.01

The mass fraction of the composition that reached the target from a distance of 3 m is 86% (1.72 g out of 2 g).

The effective throwing range is 5.5 m.

Example 1.3

According to example 1.1, characterized in that it contains two irritants - CR and 10% selective extract of red pepper (OS10), and as a thickener - cellulose triacetate (TAL), in the following ratio of components, mass. %:

Triacetin 88.0 CR 1,0 OS10 5,0 DMSO 4.9 TAC 1,0 Sudan Red G 0.1

The mass fraction of the composition that reached the target from a distance of 3 m is 86% (1.66 g of 2 g).

The effective throwing range is 6 m.

Example 1.4

According to example 1.1, characterized in that the selective extract of red pepper (OS95) was used as the irritant, and as the thickener PVA (granules), in the following ratio of components, mass. %:

Triacetin 72.5 OS95 0.5 DMSO 20,0 PVA (granules) 6,999 Sudan Red G 0.001

The mass fraction of the composition that reached the target from a distance of 3 m is 81% (1.62 g of 2 g).

The effective throwing range is 5.5 m.

Example 1.5

According to example 1.2, characterized in that the solvent contains technical triacetin (91 wt.% Tri-, 3 wt.% Di- and 1 wt.% Glycerol monoacetate), two irritants are used as irritant - CR and pelargonic acid morpholide (IPC), and as a thickener aerosil ADEG A-300 brand, in the following ratio of components, mass. %:

Technical Triacetin (91 wt.% Glycerol triacetate) 72.0 CR 1,0 IPC 5,0 DMSO 19,99 Aerosil ADEG A-300 (thickener) 2.0 Dye methylene blue 0.01

The mass fraction of the composition that reached the target from a distance of 3 m is 81% (1.62 g of 2 g).

The effective throwing range is 5.5 m.

2. Examples of compositions for the second option (without DMSO)

Example 2.1

Liquid irritant composition containing triacetin as a solvent (99.7% by weight of the main substance), irritant CR as an irritant, thickener — cellulose triacetate (TAC), a fat-soluble dye, in the following ratio of components, mass. %:

Triacetin 98.0 CR 0.99 TAC 1,0 Sudan Red G 0.01

The mass fraction of the composition that reached the target from a distance of 3 m is 90% (1.80 g out of 2 g).

The effective throwing range is 7 m.

Example 2.2

According to example 2.1, characterized in that the solvent contains technical triacetin (54 wt.% Tri-, 28 wt.% Di-, 14 wt.% Glycerol monoacetate), selective pepper extract (OS95) is used as an irritant, and as a thickener, glycerin and aerosil, in the following ratio of components, mass. %:

technical triacetin (54 wt.% Glycerol triacetate) 88.9 OS95 1,0 Glycerin (thickener) 9.0 Aerosil A-3 80 (thickener) 1,0 Dye fuchsin basic 0.1 Effective throwing range is 7 m

The mass fraction of the composition that reached the target from a distance of 3 m is 86% (1.66 g of 2 g).

Example 2.3

According to example 2.1, characterized in that the irritant is CS irritant, and as a thickener - PVA (granules), in the following ratio of components, mass. %:

Triacetin 91.5 CS 1,0 PVA (granules) 7.4 Sudan Red G 0.1

The mass fraction of the composition that reached the target from a distance of 3 m is 84% (1.68 g of 2 g).

The effective throwing range is 7 m.

Example 2.4

According to example 2.2, characterized in that the pelargonic acid morpholide (IPC) was used as an irritant, and glycerin was used as a thickener, in the following ratio of components, mass. %:

technical triacetin (54% glycerol triacetate) 84.0 IPC 6.0 Glycerin (thickener) 9.9 Dye fuchsin basic 0.1

The mass fraction of the composition that reached the target from a distance of 3 m is 88% (1.76 g out of 2 g).

The effective throwing range is 7 m.

Example 2.5

According to example 2.1, characterized in that two irritants were used as irritant - CR and selective extract of red pepper (OS95), and as a thickener PMMA "Dacryl 82", in the following ratio of components, mass. %:

Triacetin 91.0 CR 1,0 OS95 1,999 "Dacryl 82" 6.0 Sudan Red G 0.001

The mass fraction of the composition that reached the target from a distance of 3 m is 88% (1.76 g out of 2 g).

The effective throwing range is 7 m.

Thus, in all examples of the implementation of the claimed annoying composition, the effective throwing range (5.5-7 m) exceeds that of the prototype composition (3-5 m).

When throwing the proposed annoying formulations based on triacetin, the mass fraction of the formulation that has reached the goal (target) is also higher than that of known formulations, including the prototype. So according to the prototype, from a distance of 3 m when shot from BAM 13 × 60, containing 2 g of an annoying formulation, 68-76% of the liquid reaches the target. Whereas in the proposed options (see examples), the proportion of the flying recipes ranges from 81 to 90%.

It should also be noted that when testing highly colored formulations in a test room (i.e., without wind), it is seen that after firing at a target with a known prototype compound, a distinctly colored “track” from small dots on a sheet of paper spread out on the floor remains testing laboratory. That is, there is a shortage (subsidence) of very small (respectively - light) drops. With the new recipe, the "path" is almost invisible.

Claims (6)

1. A liquid irritant composition for self-defense products containing at least one irritant, thickener, dimethyl sulfoxide and an organic solvent or mixture of organic solvents, characterized in that it contains glycerol triacetate or a mixture of tri-, di- and monoacetates of glycerol as an organic solvent with a glycerol triacetate content of not less than 54 wt.%, in the following ratio of components, wt.%: irritant 0.5-6.0 glycerol triacetate or mixture glycerol tri-, di- and monoacetates 64-94 dimethyl sulfoxide 2-20 thickener 1-10 2. The composition according to p. 1, characterized in that it further contains a dye in an amount of 0.001-0.1% wt.%. 3. A liquid irritant composition for self-defense products containing at least one irritant, a thickener and an organic solvent or mixture of organic solvents, characterized in that it contains glycerol triacetate or a mixture of glycerol tri-, di- and monoacetates containing glycerol triacetate not less than 54 wt.%, in the following ratio of components, wt.%: irritant 1.0-6.0 glycerol triacetate or mixture glycerol tri-, di- and monoacetates 84-98 thickener 1-10 4. The composition according to p. 3, characterized in that it further contains a dye in an amount of 0.001-0.1% wt.%.