RU2102059C1 - Insecticide-acaricide composition, method of protection of articles and materials from keratophages, inert carrier, method of determination of composition retentivity on fabrics, method of determination of composition abradability on fabric, insecticide-acaricide composition for dress treatment - Google Patents

Abstract

FIELD: medicine, medicinal disinfection. SUBSTANCE: compositions have cyano-containing pyrethroids, fine-grade powder-like carriers of small specific gravity, filling agents, oil-like additions, binding agents, antioxidizing agent, additions enhancing effectiveness and rapid effect of composition: attractants, repellents, paralytic agents. Invention gives compositions providing 100% death of keratophages. Retentivity index for acaricides is 55-98% and that for antimoth using - 35-85%. Abradability index under pressure 0.1-0.2 kg/cm² is 15-100 mcm/1000 m. Composition has the following components, wt. -%: cyano-containing pyrethroid, 1; oil-like addition, 25; binding agent, 50; antioxidizing agent, 2; attractive addition, 0.1; repellent addition, 15; paralyzing addition, 15; and filling agent and/or carrier, 60. Compositions provide human protection from ticks and other insects. EFFECT: enhanced effectiveness of composition. 16 cl, 10 tbl

Description

 The invention relates to medicine, medical disinfestation, and relates, in particular, to protecting a person from attack by blood-sucking ticks, as well as protecting products with natural keratin (furs, wool, etc.) from keratophages of moth larvae and skin-eaters.

 Dry formulations (dusts, bars, crayons, etc.) have advantages over other forms in terms of the effectiveness of the use of the insecticaricidal active ingredient (AI) and safety for warm-blooded and human beings. However, as a rule, they are not used for processing clothes and materials. The first examples of Pretix and Pretix-M bars are used to protect a person from blood-sucking ticks and to protect materials from keratophages, respectively.

 The main disadvantages, apparently, the fragility of the processing (flaking), prejudice to the use of cyanide compounds for personal protection of a person. The property of blocking the suction functions of blood-sucking mites by the action of cyanide-containing pyrethroids, known from Russian patent N 2007161 (priority from 30.18.98, registered 15.O2.94), suggests the search for acceptable formulations based on such AI for the processing of human clothing. It also describes the types of agents suitable for processing human clothing, including cyanide-containing pyrethroid. The Russian patent (application N 93119882 dated 05/18/93, positive decision dated September 30, 1993) also describes a physiologically and functionally acceptable carrier - ultrafine grinding of natural cellulose-containing raw materials.

 An object of the invention is the creation of an effective dry insecticide and acaricide, tissues, materials for protection against crawling parasites (ticks, lice, etc.), keratophages of moth larvae and skin-eaters.

 To solve the problem, the preparative form of the insecticaricidal agent is selected so that the final form of the agent is in powder (dust) form on the treated clothes, fabrics, furs, wool in places that provide the most likely contact with the biological object being destroyed: against blood-sucking mites on the surface of the tissues on its outer villi; against lice in the folds of clothing; against larvae of moths and skin-eaters in the outer volume of a woolen product, at the base of a pile of furs. The amount of cyanide-containing pyrethroid is selected taking into account the retention of the formulation in the applied form; for briquetted forms, the abrasion index, which provides a finely divided powder form of the applied agent, is important.

An acceptable indicator of the retention of the applied means to protect against blood-sucking ticks and body lice on tissues with an amount of 0.1-1.0 mg / cm ² is 55-98%. For the protection of woolen things, furs from keratophages, this indicator is acceptable in the following interval 30- 85% (retention limits are significantly shifted towards weakening due to the need for easy removal of the particles of the product from things when they are removed from storage.

 The retention of insecticaricidal agents and other bulk materials is determined by applying the test agent to the tissue, followed by vibration with a beat frequency of 50 Hz and an amplitude of 5 mm for a given time, and the retention rate is determined as a percentage of the remainder of the agent compared to its initial amount on the fabric.

 The abrasion index of briquetted forms of insect-acaricidal agents (briquettes, crayons, bars, etc.) on the fabric with a pressure on it of 0.1-0.2 kg / cm should be 15-100 microns / 1000 m.

 To determine the briquetted product, it is fixed on the fabric under pressure, then the fabric is moved in a cyclic mode and the worn product is simultaneously removed, and the abrasion index is determined by the loss of thickness on a given route.

The effectiveness of the applied insecticaricidal agent in the final form in the form of a powder can be demonstrated on the amount of cypermethrin, which ensures blocking of the suction functions of taiga ticks Ixodes persulcatus when processing clothes according to the scheme of RF patent N 2007161:
The method of applying protective strips The amount of cypermethrin per 1 suit, mg:
Briquetted dry form 4-5
Gel formulations 300-500
Wax pencils 600-700
The impregnated patch 50-80
Continuous treatment of a suit with an aerosol or UMO 150-350
Since cypermethrin is usually the most toxic component of the composition, its toxic effects on humans are proportional to their consumption per treatment.

 The method of protecting products from keratophages by treating non-volatile solid preparative forms of contact action has novelty and advantages over the use of volatile larvicides and ovicides.

 1. The drug or the drug itself practically not inhaled by humans - adverse effects are minimized compared with typical volatile anti-mole preparations, which is especially important for people prone to allergies and asthmatics.

 2. After prolonged storage in air, pyrethroid preparations weaken repeatedly and are practically safe for humans when they are removed from products after storage. At the same time, moth larvae experience an antifidant effect on keratin-containing surfaces with sublethal concentrations of AI which allows you to either reduce the initial concentration of AI in the drug, or extend the effective protection period.

 3. The efficiency of continuous processing of products is visually controlled by the performer on dusty particles of the product remaining on things, which guarantees the destruction of existing keratophages or planted after processing.

 4. Dusty remnants of the product can be completely removed from the product with a vacuum cleaner or brush without damaging things. There is no smell left (unlike volatile preparations). The completeness of the removal of the product is monitored visually.

 Thus, taking into account the indicators of efficiency, safety for humans, abrasion and retention, a composition against keratophages was created, which is a dry preparative form in the form of a powder or in a briquetted form (briquette, crayon, whetstone, etc.), applied by spraying or layer-by-layer abrasion ( hatching), respectively. The composition includes a pyrethroid, mainly cyan-containing, with a low vapor pressure, an inert carrier, mainly ultrafine wood (UDD), other fine powders with a low specific gravity of particles, chalk, gypsum, talc, kaolin in the following ratio of components, wt.

Pyrethroid 0.05-0.3
Inert carrier Else
The remedy for keratophages may further include an oily additive, mainly vaseline or silicone oil in an amount of up to 5 wt. a binder in the form of glue, starch (paste) in an amount of up to 10% or gypsum in an amount of up to 50 wt.

 The effectiveness of the keratophage preparations is shown in the following Table 1 (the formulation from Example 1 at the end of the text), as well as the powder of the composition alphametamerin 0.03-0.1% UDD carrier 5% filler: chalk the rest).

 The tests were carried out against the caterpillars of the clothes moth and the larvae of the skin-beetle beetles on the woolen fabric when exposing the treated areas in natural light, which reduces the effective action of the pyrethroid several times compared to storage in a shaded room, which is implemented in practice with seasonal storage.

Thus, for 100% destruction of keratophages, the concentration of alfamethrin in the composition is 0.04 mg / m ² , which is 15-50 times lower in the number of d.v. than when using other preparative forms with vol. (aerosols, emulsion concentrates). For seasonal storage of things, it is enough to create on the surface of the products a concentration of alpha-metrine 0.1-0.15 mg / m ² in the developed composition. Taking into account the indicators of retention and abrasion, an insect-acaricidal composition has been created for treating human clothes, which is a solid preparative form capable of layer-by-layer abrasion, including a cyanide-containing pyrethroid and an inert carrier, mainly UDD, other fine powders with a low specific gravity of particles, chalk, gypsum, talc or kaolin, in the following ratio of components, wt.

Cyan-containing pyrethroid 0.1-1.0
Inert carrier Else
The choice of a cyanide-containing pyrethroid is based on Russian patent N 2007161 and publication in "Experimental and Applied Acarology" (UK ed., Vol. 18, N4, pp. 233-240, 1994) for the combination of factors of high toxicity against ticks and insects, lack of suction after receiving a standard dose of pyrethroid, fast knockdown, a small elevation after receiving a dose. These criteria are best met: alfamethrin and other highly effective isomers of cypermethrin and their compositions (zetamethrin, for example); highly effective isomers of cygalotrin and their compositions (for example, lambda-cygalotrin); delta metrin, flumetrin isomers and compositions thereof; indocoitrin, cyfluthrin and compositions of its isomers.

The insecticaricidal agent may additionally contain an oily non-polymerizable additive, mainly vaseline or silicone oil in an amount of up to 25%, a binder in the form of glue or gypsum in an amount of up to 50% and an oxidation stabilizer, mainly derivatives of sterically hindered phenols, in an amount of up to 2%
In addition, the insect-acaricidal composition may additionally be mite-attractive, predominantly pelargonic acid, salicylic aldehyde or 2,6-dichlorophenol in concentrations of 0.0001-0.1%, or their composition in the same concentrations. Instead of an attractive composition, the insect-acaricidal composition may include a tick repellent additive, mainly DETA, acrep-N- (hexyloxymethyl) caprolactam, orthophthalic acid esters, oxamate (aliphatic esters of N, N-diethyloxamic acid), benzimine (1,1-hexamethylbenzene) N, N-benzoylpiperidine in concentrations of 1-15%, or a combination thereof within the same concentrations.

 The insect acaricidal composition may further include a tick paralyzing additive, mainly transpiretroid acids, namely, transchrysanthemum, transflumetric, transpermetric, trans deltamethric, transcygalotric acid in concentrations of 1-15%, or combinations thereof within the indicated concentrations. In addition, the insecticide and acaricidal composition may contain both attractive and paralyzing additives or repellent and paralyzing additives at the above concentrations.

 It has been established that for effective protection against ticks and other crawling insects and parasites, a preparation based on the above cyanide-containing pyrethroids should be applied in an amount of 0.1-0.5 mg / dm by d.v. (when applied in stripes 1-2 cm wide). To protect against keratophages, the dosage can be reduced by 10-20 times. In this case, solid forms should be applied to the fabric without significant effort. Fragile, easily abrasive compositions, as well as rigid formulations are less effective. To quantify the properties of abrasion, a quantitative criterion has been developed that is determined under standard conditions for a given force and strip length. The most important condition for the operability of the applied product is a set of properties, the possibility of transition and the duration of retention on a biological object, as well as on the treated tissue. We also developed quantitative criteria for this indicator. In general, there is a dependence of the required working concentration of and retention rate. With a "good" and "very good" degree, it is minimal. For the "average" 1.5-2 times higher, for the "bad" 3 or more times higher. With "poor" retention, the advantages of dry forms are leveled. With an "average" degree of retention, the performance of the protective strips on the moving parts of the clothes lasts 1-2 hours, which is acceptable for practical use. With a "good" degree, the performance of the bands lasts 2-3 hours, with a "very good" 3-5 hours. On sedentary parts of clothing (around the neck), the strips work 2-3 times longer.

 You can also apply formulations in the form of dust on the fabric. But for powders, it is difficult to achieve uniformity of application and good retention.

 Methods for determining abrasion.

A sample of the studied tissue is fixed on a rotating disk and, at a certain distance from the center, a sample of the agent is pressed against the surface with a force of 100-200 g / cm ² . When the rotation of the disk starts, air blowing is switched on to remove the worn-out product.

 Abrasion is measured in microns of the loss of thickness of the sample of the product with a standard "mileage" of 1000 m. A good quality indicator of 15-100 microns was revealed. Products with greater abrasion are poorly held, and with less abrasion are difficult to apply.

 The method for determining retention.

 On a vibrator with a beating frequency of 50 Hz and an amplitude of 5 mm, a treated piece of tissue 10x10 cm in size is suspended. The vibration time is 5 minutes.

Quantitative characteristics (measured in the remainder of the applied funds):
weak retention 30-55
"average" retention 55-65
good retention 65-80
"very good" retention 80-98
At indicators below the "average" and above the "very good" formulation of the product is undesirable because of the rapid shedding of the product or reduced effectiveness, respectively. To protect against keratophages, the ability to completely and fairly easily remove the agent is also important, therefore the indicator of "very good" retention is undesirable, and "weak" retention is acceptable.

 The table below shows insecticaricidal compositions for treating human clothing containing type 2 pyrethroid at a concentration of 0.05-1.0%, taking into account the abrasion and its retention on the fabric, as well as the types of fabric.

 The composition may include only a pyrethroid and an inert carrier (1,6,9).

As an inert carrier are used: UDD (UDD grinding wood with an average particle size of 20-30 microns and a fraction with a particle size of less than 10 microns not less than 5 wt.), Fine grinding of lignin, grass flour, grinding of soils rich in organic compounds, dusty light industry wastes with a low specific gravity of particles, as well as chalk, two-water gypsum, talc, kaolin and others in a concentration of from 5 to 99.95%
To enhance retention and increase the plasticity of the mass of the product in the form of an article, an oily additive in the form of predominantly liquid paraffin or silicone oil in a concentration of up to 25% can be introduced into the composition
A binder in the form of glue, gypsum is introduced to cure the product in the form of a product, if it is not achieved by other methods, in a concentration of up to 50%
The oxidation stabilizer is introduced in order to extend the shelf life of the product in the form of an article and during operation to extend the effective period. The stabilizer prevents decomposition under the influence of heat and light, and oxygen in the air. and oily additives. Derivatives of 2,6-di-tert-butylphenol or other sterically hindered phenols, for example ionol, irganox 1010 in a concentration of up to 2%, are used as stabilizers.
In the table. 2 shows examples of insecticaricidal compositions for the processing of human clothing.

All formulations at the initial time allow you to apply AI on the fabric in the required concentration of 0.05-05 mg / DM ² . They are intended for processing clothes in order to protect humans from creeping arthropods and provide:
applying pyrethroid to tissue at a surface concentration of 0.05-0.5 mg / dm ² ;
abrasion within 15-100 microns / 1000 m;
retention on natural tissues within 48-96%
The same formulations with retention rates of not more than 85% can be used to protect against keratophages and provide for the application of pyrethroid at a concentration of 0.05-0.3 mg / dm ² .

 The above formulations may include well-known dry preparations (dusts, crayons) in a new field of application for clothing for personal protection of a person from creeping blood-sucking arthropods or protection of things from keratophages.

 To enhance the action against blood-sucking ticks, specific additives can be introduced into the insect-acaricidal compositions.

A. Mite-attractive additives for mites, namely pelargonic acid, salicylic aldehyde, 2,6-dichlorophenol at a concentration of 0.0001-0.1 wt. or combinations thereof at the same concentrations when introduced into the above formulations cause mites to linger for longer periods on protective strips or on treated surfaces (Table 3)
In addition, some ticks do not cross the treated zone (COD repellent coefficient). CODE for formulations without an attractant is 5-20% for formulations with an attractant up to 40% (mainly males are delayed).

 As shown in experiments with a composition containing attractive additives, Ixodes persulcatus mites at a distance of 5 cm from the concentric protective strip of the product (15 cm in diameter) bend their vertical route towards the indicated circle, some of the ticks linger on the protective strip. Dermacentor nuttali mites are more responsive to the attractant: in addition to the curvature of the route, a multiple crossing of the strip was noted, long delays on it, part of the ticks moved directly along the strip of 5 cm or more. For the recipe used in the experiment, the knockdown time for taiga ticks Ixodes persulcatus was 6-8 minutes, and for the steppe ticks Dermacentor nuttali, they were significantly large in size and weight 20-23 minutes, which allowed them to contact acaricide for so long. Thus, these attractive additives extend the contact time with the protective strips, which increases the effectiveness of the tool. In the above table. 4, formulations with and without attractive additives are compared, from which it can be seen that prolonging the contact time in the first pair allows reaching the knockdown limit value with a significantly lower content of AI and in the second pair, it demonstrates a significant increase in efficiency only from the introduction of such an additive.

 Knockdown time is typical for each AI and is of utmost importance. Under the conditions of the experiment, the knockdown for formulations 1 and 2 is the maximum possible.

 B. Repellent additive, mainly DETA, acrep, as well as cycloalkyl derivatives of benzoylimide, orthophthalic acid esters, introduced into the above formulations in concentrations of 1-15 wt. lead to the fact that the CODE of the protective bands for Ixodes persulcatus ticks increases to 60% Some of the ticks cross the strips in a few attempts, returning to untreated tissue sites. Thus, the contact time with the insectoacaricidal composition is significantly extended, and its effectiveness is increased.

Examples of CODE for formulations that differ in the amount of repellent:
Without repellent (alfamethrin up to 1%) 40%
The same DETA up to 10% 50%
The same DETA up to 20% 60%
the amount of alfamethrin is constant.

 B. Paralyzing additives for ticks, namely transisomers of pyrethroid acids: permethric, deltamethric, cygalotrin, flumetric, especially chrysanthemum acid, in a concentration of 1-15 wt. introduced into the above formulations, after ticks crossing the protective strips, the ticks stop moving in a state of stupor after 2-4 minutes, then after some time they disappear from the tissue. The average height of rise to a stop is 15-20 cm. Thus, the likelihood of ticks falling from clothing onto the human body is sharply reduced. Examples of influence are given in table. 5.

 G. To further enhance the effect of the compositions, a combination of two or more additives mentioned above under the letters A, B, and C. can be used. In addition, the value of the CODE increases and the mite route along the clothes is reduced, and the knockdown time is practically unchanged. The maximum effect is observed when combining repellent and paralyzing additives, in which the COD value can reach 75% and the height of the taiga ticks on the protective strip will not exceed 6 cm, and the crossing time is longer than the stay on the untreated surface above the bands, and the latter does not exceed 1 min . Such a composition has important properties for the product, the visibility of the effectiveness of the visually highlighted barrier: mites with great difficulty overcome the strip and fall off the clothes immediately after it, and most of them directly from the protective strips. Examples with combined additives are given in table. 6.

 The above scatter is due to differences in carrier composition.

 An important aspect of the effectiveness of the formulations is the carrier and its degree of dispersion.

 In terms of dispersion, the situation is such that the finer the particle, the higher the efficiency of the product. As a criterion, the knockdown time was chosen at the same concentration of AI

 Examples of cellulose-containing carriers for grinding wood (the concentration of alfamethrin is constant-0.1%) are shown in table 7.

 Examples for grinding soil rich in organic matter at a standard concentration of alfamethrin (up to 1%) on taiga ticks after they intersect two protective bands are shown in Table 8.

 It should be noted that the most effective fractions for carriers were obtained in the limiting regimes of grinding vortex and planetary mills, which limits their availability in terms of economic indicators.

 Comparison of carriers among themselves is difficult due to the fact that during grinding and classification they behave differently and it will be almost impossible to obtain the same fractions, however, for fractions of the maximum possible grinding of different carriers with similar specific gravity particles show approximately the same efficiency.

 With a close composition of the UDD fractions or grinding of herbs, they significantly exceed the heavier carriers (Table 9).

Additives of fractions with maximum efficiency significantly increase efficiency (on Amblyomma herbaerum nymphs 4):
Wood grinding averaged. fraction 150 μm 18.8 min
The same + 10% UDD averaged. 15 μm 15.6 min
Chalk 14.5 min
The same + 5% UDD 15 μm 10.5 min
With the same dose of AI The factor of the number of active particles determined by the concentration of the carrier is also important (Table 10).

Summarizing the above in relation to the functions of the medium, we can conclude that its maximum efficiency under the following conditions:
the maximum possible degree of dispersion of particles,
low specific gravity of carrier particles,
the maximum possible concentration of the carrier in the formulation.

One of the best carriers is ultrafine wood UDD with a particle size of 1-50 microns and a particle fraction content of less than 10 microns not less than 5 wt. Small additives of UDD significantly enhance the formulations of typical carriers - chalk, talc, and others. Moreover, noticeable effects are observed with a share of UDD even 5%
The filler function optimizes the plasticity of the formulation, the satisfaction of the abrasion, improving economic performance.

 The binder is used for molding briquetted insectoacaricidal formulations, it is selected according to technological and economic indicators.

 Given the totality of the above factors, it becomes possible to create formulations with the highest possible performance indicators (knockdown time, lift height) at the concentration of AI cyanide pyrethroid below 1 wt. which guarantees the safety of the product for humans and animals during operation.

Claims (13)

 1. Insecticide-acaricidal composition for treating human clothing, as well as fabrics and materials containing natural keratin, based on active substances, mainly cyanide-containing pyrethroids, characterized in that by means of the composition they create a protective powder layer or protective (barrier) stripes on the treated object, the amount of active substances are determined taking into account the effectiveness of the carrier, the retention of the composition on the treated surface and abrasion for briquetted forms of the composition.  2. A method of protecting products and materials containing natural keratin from keratophages, characterized in that a powder protective layer of a non-volatile preparation of a contact mechanism of action is created on the protected object by spraying the finished powder or abrading the briquetted formulation of the composition according to claim 1 on the surface of the object.  3. An inert carrier, characterized in that it is a finely divided fine powder with a fraction of particles with a size of less than 10 microns not less than 5 wt. from materials with a low specific gravity of particles, mainly ultrafine grinding of natural cellulose-containing materials, natural biological materials, products of their processing, soils with a high content of organic substances, used individually or in combination with fine powders of chalk, gypsum, clay, talc and inert safe for humans inorganic materials.  4. The carrier according to claim 3, characterized in that in the briquetted formulations of the composition according to claim 1, its content is at least 15 wt. and in powder forms at least 5 wt.  5. A method for determining the retention of powdered compositions on tissues by applying the test composition to the fabric, followed by vibration with a beat frequency of 50 Hz and an amplitude of 5 mm for a given time, and the retention rate of the composition on the fabric is determined as a percentage of its balance compared to the original amount. 6. The method according to claim 5, characterized in that the retention rate of the composition on the tissue when applied in an amount of 0.1 to 1.0 mg / cm ² is 55 98% for insect-acaricidal compositions and 35 85% for keratophagic agents
7. A method for determining the abrasion of compositions on tissue, which involves fixing the test composition on the fabric under pressure, followed by its movement and simultaneous removal of the frayed composition, and the abrasion index is determined by the loss of thickness of the test product in a given cycle. 8. The method according to claim 7, characterized in that the rate of abrasion of the composition on the fabric at a pressure on it of 0.1 0.2 kg / cm ² is for the insecticaricidal composition according to claim 1 15 100 μm / 1000 m  9. An insect-acaricidal composition for treating human clothing, keratin-containing products and materials, comprising an active substance, mainly a cyanide-containing pyrethroid and a physiologically acceptable carrier, characterized in that it is a solid abrasion-resistant formulation containing an inert carrier in the following ratio of components, wt . Active ingredient 0.05 1.0
Inert carrier Else
10. The composition according to claim 9, characterized in that it additionally contains an oily additive, mainly vaseline or silicone oil and / or a binder, mainly gypsum, adhesives, and / or an oxidation stabilizer, mainly derivatives of sterically difficult phenols, in concentrations, wt. Oily additive Up to 25
Binder Up to 50
Oxidation Stabilizer Up to 2
11. The composition according to PP. 9 and 10, characterized in that it further comprises a tick-attractive additive, mainly pelargonic acid, salicylic aldehyde, 2,6-dichlorophenol, or a combination thereof in a concentration of 0.0001 to 0.1 wt.  12. The composition according to PP. 9 and 10, characterized in that it additionally contains tick repellent additives, mainly DETA, Acrep-N (Hepsiloxymethyl) caprolactam, orthophthalic acid esters or cycloalkyl derivatives of benzoylimide, in a concentration of 1 to 15 wt.  13. The composition according to PP. 9 and 10, characterized in that it further comprises a tick paralyzing additive, mainly trans-chrysanthemum and other trans-pyrethroid acids in a concentration of 1 to 15 wt.  14. The composition according to p. 13, characterized in that as a paralyzing mite additive, it contains 1 R-trans-chrysanthemum acid, trans-permethric, trans-deltamethric, trans-cyhalotrinic, trans-flumetric acid.  15. The composition according to PP.9 and 10, characterized in that it further comprises a combination of attractive and paralyzing tick additives in a concentration of 0.0001 to 0.1 and 1 to 15 wt. respectively.  16. The composition according to PP.9 and 10, characterized in that it further comprises a combination of repellent and paralyzing mite additives in a concentration of 1 15 and 1 15 wt. respectively.

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