DK154533B - APPLICATION OF AN AROMATIC ACYLOXYCARBOXYLIC ACID AS DISINFECTIVE ACTIVATOR FOR H202 POLLUTANTS - Google Patents

Description

DK 154533 B

in

The invention relates to the use of an aromatic acyloxycarboxylic acid as a disinfectant activator for H2 O2 scavenging agents in a storage-containing mixture containing them which, when dissolved in water, gives a solution having strong antimicrobial action.

It is known that organic peracids have excellent antimicrobial effect, but their use is not without problems.

10

Admittedly, lower aliphatic monocarboxylic acids, such as peracetic and perpropionic acids, are capable of forming resistant solutions when the peracid acid content of these solutions is high. Diluted ready-to-use solutions of these acids, e.g. for 15 disinfection purposes, however, are not persistent for long periods and therefore cannot be marketed. A disadvantage of the concentrated peracid solutions is an extremely pungent odor, such as 90? the handling and use thereof is difficult and even questionable. Furthermore, by shaking or spilling these concentrated solutions, etchings, material damage or violent decomposition reactions can occur.

Other percarboxylic acids, such as the perbenzoic acid, is already volatile in itself and is therefore not commercially available.

Stable percarboxylic acids, such as The p-tert.-butylperbenzoic acid and the p-methoxyperbenzoic acid are relatively poorly soluble in water, so that the setting of a particular peracid content due to the low dissolution rate requires a considerable time.

In addition, organic peracids in neutral and alkaline environment are generally not stable for extended periods of time.

From DE patent application 807,122 it is known to prepare bactericidal agents by melting non-toxic esters of p-oxybenzoic acid with sodium perborate or sodium percarbonate, which at 2

DK 154533 B

solution in water shows a better disinfectant effect than a simple p-oxybenzoic acid. However, the melting of these components means a considerable thermal load on the system and leads to side reactions in which by-products which are undesirable in the disinfectant are formed. In addition, the melting of inorganic per-splitting agents with organic matter is not harmless.

SUMMARY OF THE INVENTION The object of the invention is to provide a disinfectant activator for use with H 2 O 2 scavenging agents in a solid formulation composition which, immediately before use, dissolves in water to give a solution with a high percarboxylic acid content and good disinfectant. , antimicrobial action.

15

The invention therefore relates to the use of an aromatic acyloxy-carboxylic acid of the general formula

ISLAND

island

O-C-R

20 I

fl ^ l

-i-COOH

Wherein R represents a phenyl group optionally substituted with halogen atoms, lower alkyl or alkoxy groups, wherein the carboxyl group may be ortho-, metha- or para-substituted to the acyl oxy group, or water-soluble alkali, alkaline earth or ammonium salts thereof, wherein up to 4 of The hydrogen atoms of the ammonium cation may be substituted by alkyl groups as a disinfectant activator for H2 O2 scavengers in such a mixture.

These derivatives of the aromatic acyloxycarboxylic acids are also referred to as carboxyphenylbenzoic acid derivatives hereinafter.

During the dissolution of this mixture and also some time after a clear solution has already been formed, eye-sighting occurs.

DK 154533 B

3 equals a reaction between the carboxyphenylbenzoic acid and H2O2 in that, during cleavage of the ester linkage, free hydroxybenzoic acid and perbenzoic acid are formed, and in an alkaline solution a certain peracidic content is not maintained for a long time, period of time. It seems to be essential for this that the ester cleavage does not proceed spontaneously, but requires a certain amount of time and thus ensures a high peracid content for a longer time. If, on the other hand, the single components that are dissolved in the mixture, i.e. percarboxylic acid and aromatic hydroxycarboxylic acid, were combined with each other, neither in solid nor in liquid form would a storage stable product be obtained, especially in the pH range of the solution preferred from 4 to 12. The mixtures and the solutions obtainable therefrom are soluble. those properties which do not exist in a combination of the single components that arise when dissolving the mixtures.

The mixtures dissolve particularly rapidly when using water-soluble salts of the carboxyphenylbenzoic acids.

20

The carboxyphenylbenzoic acids or their salts and the H 2 O 2 scavenger are not so reactive that they already react with each other in a solid state, but they are sufficiently reactive to immediately react with fast dissolving into vigorous, powerful solutions. effective perbenzoic acid and to the corresponding hydroxycarboxylic acid with long-term antimicrobial action.

The cleavage of the ester bond is favored by an alkaline environment. Particularly suitable is the pH range of 8-12, which is also optimal for a purifying effect of the mixture.

However, the amount of alkaline reacting constituents in the mixture can also be adjusted so that, by cleavage of the ester, the alkaline constituent is consumed by neutralization of the perbenzoic acid and hydroxycarboxylic acid, thereby forming a neutral solution. By "neutral solution" in the present case is meant a solution having a pH value of 4 to 8.

4

DK 154533 B

This pH range is more advantageous for the persistence of the organic peracids than an alkaline pH range.

Suitable water-soluble salts of the carboxyphenylbenzoic acids are the 5 lithium, sodium, potassium, ammonium and magnesium salts thereof, wherein 1, 2, 3 or all 4 hydrogen atoms in the ammonium cation may be substituted by alkyl groups. Sodium, potassium, ammonium and substituted ammonium salts are preferred.

Examples of aromatic acyloxycarboxylic acids useful in the invention are benzoyl, (4-methoxybenzoyl) -, (3-chlorobenzoyl) -, (4-tert-butylbenzoyl) - and (4-methylbenzo-yl) -salicylic acid, 3- benzoyloxy, 3- (4-methoxybenzoyloxy) -, 3- (3-chlorobenzoyloxy) -, 3- (4-tert.-butylbenzoyloxy) - and 3- (4- methylbenzoyloxy) -benzoic acid and 4-benzoyloxy-, 4 - (4-methoxybenzoyloxy) -, 4- (3-chlorobenzoyloxy) -, 4- (4-tert.-butylbenzoylloxy) - and 4- (4-methylbenzoyloxy) -benzoic acid, wherein benzoyl-, (4- methoxybenzoyl) and (4-tert-butyl benzoyl) salicylic acid, 3-benzoyloxy and 3- (4-methoxybenzoyloxy) -benzoic acid, and 4-benzoyloxy- and 4- (4-methoxybenzoyloxy) -benzoic acid are preferred.

As H 2 O 2 scavengers for use in the invention, "α1 a1" in "perborates," alkali "percarbonates," alkali "perphosphates," alkali "peroxides," alkali "salts are suitable

Car'schenic acid, "alkali" salts of peroxide sulfuric acid and percarbamide, which means "alkali" are salts of lithium, sodium, potassium and ammonium. The water-soluble salts of the carboxyphenyl benzoic acids disclosed in the mixtures possess high solubility and high dissolution rate in water, are easy to prepare and have a higher melting point than the corresponding acids.

This high melting point is of particular importance for the practical application. Otherwise, during storage there may be a clumping of the mixture, e.g. by the action of sun rays or storage at elevated temperature. The sodium salt of the benzoyl salicylic acid has e.g. a melting point above 300 ° C.

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DK 154533 B

Thus, the salts of the carboxyphenylbenzoic acids ideally meet the requirements for trouble-free storage without clumping, which, in the rapid and uniform dissolution of the mixture in water or aqueous systems, would seem very unfortunate.

5

The organic peracid formed by solution has an excellent antimicrobial effect which occurs very quickly. The germicidal effect of the peracid immediately occurs is very important for the practical use of the mixture as a disinfectant, since the organic peracids under the conditions are in practice not stable for a long time but gradually under the catalytic effect of metal ions, enzymes or other catalytic agents are decomposed into oxygen and the corresponding carboxylic acid.

15

In addition, it is of particular importance for use in the practice of the mixtures that the second component of the ester cleavage, ie. the hydroxybenzoic acid itself, has antimicrobial action. Its mode of action cannot be compared to the percarboxylic acid which leads to a rapid germination. However, the hydroxybenzoic acid exceeds the perbenzoic acid in terms of long-term action.

The amount ratio of carboxyphenylbenzoic acid to H 2 O 2 peel-off agent may vary within the blends within wide limits. Thus, a weight ratio of 1:10 - 10: 1 can be used. This ratio is preferably 1: 4 - 4: 1.

The mixture may also contain organic and inorganic salts to adjust and stabilize the pH of the solution prepared from the mixture. Such salts are e.g. alkali phosphates, alkali pyrophosphates, alkali polyphosphates, alkali tripolyphosphates, alkali carbonates, alkali bicarbonates, alkali calorates, alkali acetates, alkali citrates, alkali lactates and alkali tartrates. These inorganic and / or organic salts may be included in the mixtures in an amount of 1 - 90% by weight and preferably of 5 - 80% by weight.

Also, detergents which increase the wetting and purifying effect of the solutions prepared therefrom can also

. DK 154533 B

e is added, e.g. anionic detergents, especially alkyl sulfates such as coconut fatty alkyl sulfates and sebaceous fatty alkyl sulfates, alkyl sulfonates such as lauryl sulfonate, alkylaryl sulfonates such as alkyl benzene sulfonates having 8-14 carbon atoms in the alkyl moiety, soaps of natural or synthetic fatty acids, alkyl ethers and alkyl fatty acids, laurylalkoholsulfosuccinat; nonionic detergents, in particular alkylphenol polyglycol ethers such as nonylphenol polyglycol ether, fatty alcohol polyglycol ether, fatty acid polyglycol ester, polyoxypropylene glycols (Pluronics), amine oxides such as dodecyldimethyl amine sulfides and betaines such as carboxy

The weight ratio of these substances in the mixtures may be 0.5 -80% by weight and preferably 1-50% by weight.

Substances may also be included which increase the stability of the organic peracid formed by the hydrolysis, e.g. complexing agents such as ethylenediaminetetraacetic acid and its alkali salts, nitrile triacetic acid and its alkali salts, alkali salts of metaphosphoric acid, alkali salts of polyphosphoric acid, water-soluble salts of high molecular weight polycarboxylic acids, alkylphosphonic acids, dialkylphosphonic acids, dialkylphosphonic acids -dicarboxylic acid or pyridine-2,6-dicarboxylic acid.

At the same time, some of these substances have the task of complexing to bind heavy metal ions which can give colored complexes with the carboxyphenylbenzoic acids, while others, by binding the alkaline ions causing the water hardness, make the water soft. Said substances may be included in the compositions in an amount of 0.5-80% by weight and preferably of 2-20% by weight.

Inactive fillers may also be added, e.g. alkali sulfates, alkali chlorides, alkali silicates, carboxymethyl cellulose and water-soluble salts of aromatic sulfonic acids such as the benzene, toluene, xylene and cumensulfonic acid. These substances,

DK 154533 B

7, which is also intended to bind water to prevent clumping of the mixture due to the humidity of the air, released crystal water or other H 2 O sources can be used in an amount of 0.5 - 80 wt% and preferably 2-20 wt% in blan-5 things.

In addition, corrosion inhibitors, perfumes and additional antimicrobial agents can be added. Suitable corrosion inhibitors are benzotriazole, alkali phosphates, alkali hexamethosphates, alkaline nitrates, alkyl phosphates, amine oxides, ammonium soaps, sodium silicate, sodium benzoate, sodium fluoride and alkyl sulfamidocarboxylic acid. The amount of corrosion inhibitors may be 0.5 - 30% by weight, preferably 1-20% by weight.

As additional antimicrobial agents, carboxylic acids such as benzoic acid, salicylic acid and sorbic acid are suitable for phenols such as 2,6-dimethyl-4-bromophenol and o-phenylphenol.

The solutions that can be prepared from the blends are suitable for disinfecting and cleaning instruments, tools and articles, wall and floor surfaces and other surfaces in the hospital, medical practice, veterinary, household, industrial and public work areas and health sectors.

25

The mixtures may be in the form of powders, granules, tablets and other shaped solid substances. The mixtures and their aqueous solutions are practically odorless. In addition, as a further advantage, the solutions are tasteless, physiological and toxicological without risk.

The antimicrobial effect of the solutions obtained from the mixtures is shown in the following Tables 1 and 2.

35 The bacteriological studies were conducted according to the guidelines for the testing of chemical disinfectants (DGHM).

DK 154533 B

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The tables show:

The broad spectrum of antimicrobial efficacy, also against fungi, the long duration of action (usually required for a useful disinfectant solution, a shelf life of about 1 day), and the excellent capacity for egg white (serum).

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Claims (2)

The antimicrobial effect was investigated after DGHM. However, this was negligible in comparison with the mixtures according to the tables above. Claims. Use of an aromatic acyloxycarboxylic acid of the general formula O Wherein R represents a phenyl group optionally substituted with halogen atoms, lower alkyl or alkoxy groups, wherein the carboxyl group may be. in the ortho-, metha- or parastyl 11 to the acyloxy group, or water-soluble alkali, alkaline earth or ammonium salts thereof, in which up to 4 of the hydrogen atoms of the ammonium cation may be substituted by a 1 coolant groups as a disinfectant activator for H containing them and which, when dissolved in water, give a solution of potent antimicrobial action.