SK449890A3 - Effervescent particle biocidal and particularly viricidal agent - Google Patents

Abstract

An effervescent particulate biocidal, and in particular virucidal, composition comprising: a water-soluble inorganic halide, a strong oxidising agent which, in aqueous solution, reacts with the halide to generate hypohalite ions, sufficient sulphamic acid to act as a halogen acceptor, a water-soluble carbonate or bicarbonate, and sufficient excess sulphamic acid to react in water with the carbonate/bicarbonate to produce carbon dioxide and hence the required effervescence.

Description

BACKGROUND OF THE INVENTION Concerning compositions providing stable acid systems, there is a very broad aspect of DuPont's GS 932 750. However, the compositions described in this patent are highly volatile in powder form and release chlorine gas over a short manufacturing period. This is particularly the case because high concentrations of sodium hydrogen sulphate and mineral acid salts are used in their manufacture, which are added to achieve the desired level of acidity. The use of acidifying agents based on mineral acids causes both the instability of the preparation and also makes it '

Highly corrosive.

Another publication is G3 patent no. No. 2,073,522 to the same author as the present invention. According to this patent, the deficiencies of the DuPont patent are eliminated by using as low a .fr * acid concentration as the chlorine acceptor.

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The desired acidity at the application dilution is achieved by adding an acidifying agent selected from the group consisting of non-reducing organic acids, such as malic acid or succinic acid, or alternatively hydrogen phosphate in combination with amido-sulfuric acid. These substances produce a relatively stable, pulverulent system that does not release chlorine gas either when stored for long periods at 37 ° C or when the product is dissolved in water to a suitable approved concentration / as determined by odor or visual assessment ?. However, chlorine can be released from the formulation under wet conditions, or if instructions for use are not followed and concentrated solutions are produced. G3 patent no. 2,164,851 to the same applicant as the present invention. According to this patent, the hypochlorite is replaced by a mixture of inorganic chloride and an oxidizing agent to form hypochlorite ions in aqueous solution. A modified version of this solution is disclosed in the same applicant as the present invention, according to which a further improvement is achieved by strictly controlling the amount of the various components of the mixture. In said patent, a dry particulate composition, water-soluble and containing

- 0,01 to 5 parts per million water soluble inorganic halide,

- 25 to 60 parts by weight of an oxidizing agent which, in aqueous solution, reacts with the halide to form hypochlorite ions,

3 to 8 parts by weight of amidosulphuric acid,

up to 20 parts by weight of a non-reducing organic acid; and

10 to 30 parts (by weight of anhydrous alkali metal phosphate, the pK of its 1% by weight aqueous solution being in the range of from 1.2 to 5.5.

These compositions have proven to be very useful, but there are cases in which their physical form, i. the form of a dry, pulverulent particulate matter is not as suitable as it could be. For example, a well-known phenomenon which is associated with such compositions is dustiness, which is manifested by irritation and can also lead to eye damage and the like.

Therefore, it has become common practice to manufacture such powders into tablets. This has several advantages, for example, it is possible to substantially refine the dosage, to remove the dustiness, to disperse without weighing, and to easily control the substance and its use. Tablets are particularly useful in hospitals, as there is a great need for accurate dosing. medicine.

However, a relatively small tablet hardly achieves a high concentration of the composition required for a high level of biocidal activity, which is necessary for the composition to have a broadband effect against all possible viruses currently causing infections worldwide. Typically, tablets are made using three-percent systems, for example using citric acid and bicarbonate. Although this system works well, the tablets are relatively large. Such tablets are not only difficult to read directly for smaller animals, such as poultry, but take much longer than desired when added to, for example, drinking water for chickens where these tablets are added in addition to or instead of adding to dry food.

The use of, for example, adipic acid results in faster solubility, but leaves an unpleasant residue which is unacceptable, for example, in medical applications.

Typically, the compositions of the invention include reagents which interact with each other when the tablet is placed in water to form carbon dioxide, which is essentially a preservative. The efficacious reaction aids in tablet disintegration and solubilization of the other tablet components.

Typical reactants for this purpose are sodium hydrogen carbonate and organic acids, e.g.

- 6 lemon, adip or wine. Using these organic acids, however, the reaction gives rise to sodium salts - citrates, adipates or tartrates, which are salts of weak acid and strong base, which act as buffers, stabilizing the pH of the solution at a preferably high value. Therefore, it is not possible to obtain solutions having a low pH, which is, as explained above, particularly important from a virological point of view.

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The present invention makes it possible to produce these biocidal but essentially broadband formulations in the form of tablets which, when dissolved in water, provide a low pH solution by not using an organic acid such as citric acid, etc., but instead an inorganic amidosulfuric acid. / (Formula

Despite the fact that the use of amidosulphuric acid is in clear contradiction with the knowledge obtained in the aforementioned earlier patents, the amount of amidosulphuric acid should be such that amidosulphuric acid still acts as a chlorine acceptor but does not cause the instability of the formulation /, it was surprising It has been found that a suitable excess of amidosulfuric acid together with a carbonate or bicarbonate provides an excellent formulation suitable for the manufacture of tablets which still has the desired stability as far as chlorine release and biocidal activity are concerned.

- 7-Essence

SUMMARY OF THE INVENTION The present invention provides an effervescent particulate biocidal and, in particular, a viricidal composition, comprising:

- 0,01 to 5 parts by weight of water-soluble inorganic halide,

25 to 60 parts by weight of a strong oxidizing agent which reacts with the halide in aqueous solution. to form halogenated ions,

5 to 25 parts by weight of a water - soluble carbonate or bicarbonate, and

1 to 2 C parts by weight of amidosulfuric acid, as a halogen acceptor, for reaction with a carbonate or bicarbonate in water to produce carbon dioxide causing effervescence.

Halogen refers to halogens, such as hypochlorite, bromate or iodate.

A preferred inorganic halide is sodium chloride, which is preferably used in an amount of from 0.01 to 5 parts by weight, in particular from 0.2 to 2 parts by weight, when the composition is to be dissolved. in water from a normal home source. But can they be used? as well as other halides such as potassium chloride, bromide or iodide or sodium bromide or iodide.

The oxidizing agent used is conveniently peroxosulphate or peroxophthalate (especially potassium monoperoxophthalate), preferably in an amount of from 25 to 60 parts by weight. However, a preferred oxidizing agent is a commercially available potassium peroxosulfate triple salt, the composition of which can be represented by the approximate formula 2XHSO4 * KHSO4 * SO4 (mass ratio 45: 25: 30).

Other oxidizing agents may be used in equivalent amounts due to their oxidizing power. The oxidation power of the products of this type is expediently measured on the basis of the amount of iodine released in the reaction with potassium iodide (iodine determined by titration). This procedure is the standard procedure used in this process, and the results can be expressed in terms of the amount of useful halogenate, halogen or oxygen, or simply in the form of an oxidizing power.

The carbonate or hydrogen carbonate is suitably used in an amount of from 5 to 25 parts by weight and, in particular, many of the typical carbonates and bicarbonates have proved to be satisfactory, in particular, alkali metal hydrogen carbonates, in particular sodium hydrogen carbonate.

Amidosulfuric acid is used both as a halogen acceptor and as an acid for reaction with bicarbonate or carbonate to prepare carbon dioxide. Suitably, about 3 to 8 parts / weight and as a halogen acceptor are used

3 carbon dioxide generators of about 7-12 parts by weight of amidosulfuric acid. Thus, the total amount of amidosulfuric acid is the sum of both of these amounts, which are at least 10 to 20 parts by weight.

To improve tableting properties, the effervescent formulation of the invention may comprise a binder capable of freely binding particles that are compressed in a tablet press. íínožstvo the binder used is generally of the order of from C 5-2 dielovľhmotnostných a suitable SDojivom as magnesium, sodium L ^{r and} s ° ^dl-based fatty Acid, and polyoxyethylene / poiyglykol / and mixtures of.

In a preferred embodiment, the present invention provides a dry, particulate, water-soluble, virulent composition, comprising:

- 0,01 to 5 parts by weight of water-soluble inorganic halide,

- 25 to 60 parts by mass of the oxidizing agent which reacts with the halide in aqueous solution to form hallanlanate ions,

- 5 to 25 parts by weight of water-soluble carbonate or bicarbonate,

0 to 20 parts by weight of amidosulphuric acid and a

- binder, no

Wherein the pH value of the aqueous solution of this composition with concen?

% by weight is in the range of from 1.0 to 5.0, preferably from 1.2 to 4.0.

. The inventive composition may contain a number of additional components, in particular anhydrous alkali metal phosphates, preferably in an amount of from 10 to 30% by weight, non-reducing organic acids (preferably in an amount of up to 20 parts) to improve its various other properties. Preferably, in the presence of anhydrous surfactants in an amount of up to 20 parts by weight.

Sodium hexametaphosphate (also known as sodium polyphosphate) may be used as the alkali metal phosphate. Other phosphates which can be used partially or completely to replace sodium hexametaphosphate include tetrasodium pyrophosphate and the corresponding potassium compounds.

Phosphates act as buffers and as chelating agents, and in combination with a flat pH curve of amidosulfuric acid allow the composition to be effective over a wide range of application conditions. For example, the composition can be dissolved in hard water without adversely affecting its virulence properties.

Kereducing organic acid can be defined as an organic acid that does not reduce the oxidation power of a 1% aqueous solution of the test mixture comprising 50 parts / weight of potassium persulfate triple salt, characterized above, 45 parts by weight of sodium chloride and 5 parts of amidosulphuric acid, 20 parts by weight are added to this solution and allowed to act for 30 minutes. Preferred organic acids include malic acid and succinic acid.

Any surfactant which is compatible with acids and oxidizing agents but a particularly effective surfactant is sodium dodecylbenzenesulfonate can be used. Other suitable surfactants include lysuryl ether sulfates, condensates of alkylphenols with ethylene oxide and / or propylene oxide, polyglycol ethers of fatty alcohols, condensates of fatty acids with ethylene oxide, polyglycol ethers of alkylphenols and fatty alcohol ethoxylates. The addition of a surfactant to the composition provides an important advantage in that at least at its high content, a composition is obtained which can be used for cleaning and disinfection in a single operation.

The inventive compositions according to the invention are suitable for tabletting and can be processed into tablets by any suitable technology. The bed is thus placed in the die of a tablet press and then compressed into tablets. In principle, tableting is carried out in a completely conventional manner and therefore the technology used does not need to be further elaborated here. It is only to be understood that the invention naturally also relates to tablet formulations.

The manufactured tablets may be added to water immediately prior to use and at the site of use to form a biocidal aqueous composition of the desired concentration. The presence of phosphate in the formulation contributes to prolonging the life of the aqueous formulation and improving its dissolution performance in hard water. Phosphate causes the sequestration of any metal ions present that could cause rapid decomposition of the oxidizing agents present in the solution.

The aqueous formulation is a biocide with a broad spectrum of activity. Although the method of virus degradation is not known, it is believed that the lipoprotein cytoplasmic membrane or the outer lipid protective layer of the virus is initially ruptured, thereby exposing the EJA or DNA core of the virus. Sulphamic acid acts as a chlorine acceptor which maintains chloro stcve the birth of the solution as an addition product of ts * ^M * · sulfamic acid, and thereby prevents its release in the form of chlorine gas. Prevention of chlorine release without reducing the bacteriocidal activity of the composition is achieved by keeping the chloride or other halide in the composition at a low concentration.

In the above-cited GB patent no. No. 2,137,093 discloses details relating to the virididal activity of the composition described in this patent. Tests have shown that the addition of carbonate or bicarbonate, an additional amidosulfuric acid, and a binder has no significant adverse effect on bacteriocidal activity.

DETAILED DESCRIPTION OF THE INVENTION

Examples 1 to 3

Preparation of effervescent viricidal tablets

The virulidal agent is prepared by mixing together the following ingredients (amounts are given in parts by weight):

Folder Example

1 2 3 sodium chloride 1.5 1.5 1 monopersulfate potassium 50 50 50 acid sulphamidic 12.5 15 20 sodium sodium 10 10 10

The composition is prepared in the form of a powder mixture, from which tablets of about 3 g in weight are then prepared by conventional tabletting technology. Tableting can be facilitated by the addition of sodium stearate (about 3% by weight) and polyethylene glycol (about 6% by weight).

When the resulting tablets are disposed of in water, an effervescent reaction occurs, releasing carbon dioxide. The effervescent reaction aids in disintegration and solubilization of the tablet.

-10i j

When the tablet is placed in tap water in an amount of < 5 > sufficient to form a "% by weight " composition, the pH of the resulting solution is 2.6. .1

A

Viridic activity of the various compositions of the invention!

ä has been tested using the standard test procedures of the British Agriculture, Fisheries and Food Administration (AFA) and the Animal Virus Research Institute (AVPI). Tests have shown the efficacy of the compositions against the following broad spectrum of viruses and viral infections. At the dilution shown in the following table, the composition of Example 1 gave a log four-fold reduction in virus titer.

T a. b u i k

virus type viral infections dilution ' Adenoviridoe infertility syndrome 1: 100 Eerpetoviridae infectious bovine rhinitis trachitis 1: 600 Aujezsky's disease 1: 23C herpes cats 1: 2C0 iridoviridae African swine fever 1: 200 Parvoviridae dogs parvovirus 1: 50 Coronaviridae transmissible gastroenteritis 1: 45C avian infectious bronchitis 1: 280 canine coronavirus 1: 100 Poxviridae pseudokiahne beef cattle 1: 300

- 1Č -

virus type viral infections dilution ť Orthomyxoviridae bird flu 1: 320 Ä ? Paramyxoviridae Newcastle disease 1: 280 5 λ r T restlessness 1: 28C r j Picornaviridae vesicular disease with pigs 1: 200 foot-and-mouth disease 1: 1300 P.eoviridae Gumboro 1: 250 Eetroviridae Maedi & Visna 1: 400 AIDS 1: 200 Rhabdoviridae rabies 1: 280 Togaviridae equine arthritis 1: 350

The results obtained are the same as those obtained with the composition of GB-No. No. 2,187,098, which shows that treatment of the effervescent composition does not impair its bactericidal activity.

Tests have also been carried out to determine the short and long term stability of the tableted formulation, whose ingredients were mixed in a dry state. In these tests, the compositions were stored at 37 ° C in a sealed container from which periodic samples were taken. Typical results found with the composition illustrated by the example are shown in the following table:

- 1 <> -

time / Days / oxidative power, expressed as and and Λ and * · £ 4 number usable chlorine in -% 0 10.42 • i * 4 2 10.38 » 4 10.44 7 10.37 14 10.45 21 10.50 28 10.41

Variations in the percentage of usable chlorine are within the expected experimental error and show that the composition has excellent short-term stability.

Claims (4)

PATENTOVÉ. E ^ 6% particulate biocidal with particularly a viricidal agent, characterized in that it comprises 0.01 to 5 parts by weight of a water-soluble inorganic halide, 25 to 60 parts by weight of a strong oxidizing agent which reacts with the halide in aqueous solution to form halogenated ions, 5 to 25 parts by weight of water - soluble carbonate or bicarbonate, and 1C to 20 parts by weight of amidosulphuric acid as a halogen acceptor for reaction with a carbonate or bicarbonate in water to produce carbon dioxide causing effervescence. in/ An effervescent particulate biocidal and in particular virulidal composition according to claim 1, further comprising a binder, wherein the pH of the aqueous solution of said composition at a concentration of 1% by weight is in the range of from 1.0 to 5, 2 to 4.0. Effective particulate biocidal and especially virulidal composition according to claim 1 or 2, characterized in that the inorganic halide is sodium chloride, which is present in an amount of from 0.1 to 5 parts by weight. - <y 4. A particle biocidal and in particular a viricidal composition according to any one of the preceding claims, characterized in that:. The return comprises an anhydrous alkali metal phosphate in an amount of from 10 to 30 parts by weight, non-reducing organic acid, in an amount of up to 20 parts / weight and an anhydrous, surfactant, effluent, in an amount up to parts by weight.