DE2725067A1 - ALCOHOLIC DISINFECTANT WITH SPORICIDAL EFFECT - Google Patents

Description

Schülko & Mayr

Roberf-Koch-St.raße 2 (13943)

2OOO Killerstcdt Hamburq, the ? .. June 1 ^ 77

Alcoholic disinfectant with a sporicidal effect.

It is: known that alcohols and alcohol-containing solutions are disinfectants with a rapid onset of action. They dry quickly, leave no residue, can be handled without problems, are harmless from a toxicological point of view and hardly cause any corrosion. Areas of application for alcoholic disinfectants are 7, .Ii. hand disinfection, skin disinfection, surface disinfection and instrument disinfection.

Alcoholic disinfectants, however, have some serious ones Disadvantages on. Alcohol acts quickly and effectively on the vegetative forms of bacteria and fungi, However, bacterial and fungal spores are not killed. .Spores can survive and transmit in alcoholic solutions will. An essential requirement when using alcoholic disinfectants is therefore only to use spore-free alcohol. This requirement is with

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Reprinted by the Federal Health Office.

Another disadvantage of alcoholic disinfectants is that the alcohol used as the active ingredient is volatile and evaporates quickly and residue-free from a wetted surface. On such a disinfected surface, it can, for example, be caused by fly germs contamination and bacterial growth occur again. It would therefore be desirable to use alcoholic disinfectants to put germ-inhibiting active substances, which after the evaporation of the alcohol a thin film with growth-inhibiting effect against microorganisms.

A number of ways are known to make alcoholic solutions spore-free. The main methods are physical type, such as sterile filtration, irradiation with ultraviolet or short-wave rays and sterilization in a high pressure autoclave. These methods are relatively expensive, cumbersome, time-consuming, not universally applicable, and frequent also not sufficient, e.g. if there is a possibility of renewed contamination after sterilization.

Among the chemical methods for the sterilization of alcoholic solutions are the use of ethylene oxide or ß-propiolactone to call. Both methods are not to be used because of the toxicity and the difficult handling of the compounds mentioned recommend. In addition, both compounds can react with alcohol to form ineffective substances.

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Aliphatic dialdehydes, such as glutaraldehyde, have sporicidal activity, which is particularly good in alkaline Milieu comes into its own. Their effectiveness is increased by alcohol. Disadvantages of the alkaline alcoholic Dialdehyde solutions are the intense unpleasant odor, the limited shelf life of the dialdehyde and the inadequate Effect when using low aldehyde concentrations for a residue-free or low-residue Drying of the preparation are necessary.

It would therefore be desirable if alcoholic solutions could be made autosterile by adding a substance to the solution there, which does not significantly affect the properties of the solution, kills all germs in a sufficiently short time and then degraded by reaction with the alcohol or by decomposition, the latter two being mentioned Conditions are not absolutely necessary.

It would also be desirable if the alcoholic disinfectant would contain a highly effective sporicidal active ingredient that the disinfectant not only against the vegetative Forms of bacteria and fungi but also makes it effective against their spores. The concentration of the sporicidal agent in the alcoholic disinfectant should be measured so that after the alcohol or the evaporation Water from the treated goods to be disinfected only a very small residue remains. These demands are only

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fulfilled by a highly effective sporicidal agent. In addition, it would be desirable that this low residue on the treated Gut has a growth-inhibiting effect against microorganisms in order to prevent germs occurring even after disinfection to combat effectively.

It has now been found, surprisingly, that highly effective alcoholic disinfectants have an excellent effect against spores can be obtained when using organic percarboxylic acids or substances that dissolve organic percarboxylic acids generate, to alcoholic disinfectants there.

It is also essential for the invention that the added percarboxylic acids or the percarboxylic acids formed during dissolution develop good sporicidal activity even in very low concentrations, so that after evaporation the volatile Components only a very small residue remains on the disinfected or sterilized material, and the added ones Percarboxylic acids or the resulting percarboxylic acids when dissolving are odorless or low-odor, so that neither the smell of the alcoholic disinfectant nor the smell of the disinfected or sterilized material is adversely affected.

The added percarboxylic acids or those formed during dissolution

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break down over time into the carboxylic acids on which they are based and oxygen, which causes oxidation reactions in the solution. An important feature of the invention is that the through the decomposition of the percarboxylic acid resulting carboxylic acid has a growth-inhibiting effect against microorganisms and thus on the disinfected or sterilized material in very finely divided form develops a long-term effect.

The addition of the percarboxylic acids according to the invention or of Materials that form these percarboxylic acids when dissolved, to alcoholic solutions accordingly leads to the alcoholic solution

1.) becomes spore-free and is therefore auto-sterile, which is required for many areas of application,

2.) due to the antimicrobial effect of when the Percarboxylic acids resulting carboxylic acids develop long-term effects against microorganisms, and

3.) practically unaffected in their odor properties is because the added percarboxylic acids or those formed during dissolution are odorless or have little odor.

It is known that organic percarboxylic acids are strong oxidizing agents and can react with alcohols. The percarboxylic acids become the carboxylic acids on which they are based reduced and the alcohols to the corresponding carbonyl compounds or carboxylic acids are oxidized. However, it has been found that under the conditions under which alcoholic disinfection

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Medium are usually used, e.g. in the temperature range from about 0 to 40 C, the percarboxylic acids only very much react slowly. The percarboxylic acids can therefore develop their sporicidal effectiveness in alcoholic solutions maintain this effectiveness over a long period of time. As the organic percarboxylic acids in alcoholic solutions but not indefinitely, it makes sense to produce the alcoholic sporicidal disinfectant in such a way that that the organic percarboxylic acid is added to the alcoholic solution just before it is used as a disinfectant clogs. The alcoholic sporicidal disinfectant produced in this way then acts over a longer period of time of up to 4 weeks. The percarboxylic acid content can be determined iodometrically in a simple manner. This increases the Security of the procedure.

The percarboxylic acids used according to the invention must

a) have good sporicidal effectiveness,

b) be odorless or odorless and

c) have a growth-inhibiting effect against microorganisms.

Examples of such percarboxylic acids are:

I aromatic monopercarboxylic acids of the general formula

COOOH

^ O f-R

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in which R is in the ο-, m- or p-position to the percarboxylic acid group and is hydrogen, halogen, a straight-chain or branched alkyl radical with 1 to 4 carbon atoms, -OH, -OR, trifluoromethyl-, -SO ₃ H, -COOH, - COOR ¹ , -SO R ¹ or a phenyl radical, where R is a straight-chain or branched alkyl radical having 1 to 4 carbon atoms, and / or

II persorbic acid, perglutaric acid, succinic acid, permaleic acid, Perlactic acid, percitric acid, peracetylcitric acid, permethoxyacetic acid, perethoxyacetic acid and perdiglycolic acid.

These percarboxylic acids can be added as such to the alcoholic solutions, if appropriate in the presence of hydrogen peroxide which stabilizes these percarboxylic acids. However, they can also be added in the form of substances which only form percarboxylic acids when they are dissolved. Examples of such substances are solid mixtures of H ₂ O ₂ releasers and carboxylic acid anhydrides, carboxylic acid esters or carboxylic acid amides. The carboxylic acid anhydrides are the pure or mixed anhydrides of acids on which the percarboxylic acids listed under I and / or II are based. As carboxylic acid esters, the esters of these acids with alcohols or phenols come into question, preferably with alcohols or phenols, which themselves have a growth-inhibiting effect against microorganisms, such as the ester of benzoic acid with 2-hydroxybenzoic acid (= 2-benzoyloxybenzoic acid), which in the presence of H _? 0 _{2 is} split into perbenzoic acid and salicylic acid. Suitable carboxamides are those with weakly basic nitrogen compounds.

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Examples of aromatic percarboxylic acids of the general formula I are:

Perbenzoic acid, m-chloroperbenzoic acid, p-tert.-butylperbenzoic acid, p-Methoxyperbenzoic acid, 2-hydroxyperbenzoic acid, 4-hydroxyperbenzoic acid, 3-trifluoromethylperbenzoic acid, monoperphthalic acid

Examples of H ₂ O ₂ releasers are:

Alkali perborates, alkali percarbonates, alkali perphosphates, alkali peroxides, percarbamide, peroxodisulphates, peroxomonosulphates,

Examples of carboxylic acid esters are:

2-benzoyloxybenzoic acid, 3-benzoyloxybenzoic acid, 4-benzoyloxybenzoic acid, 2-hexadiene (2 ', 4') - oyloxybenzoic acid and their Alkali salts, lactide (cyclic ester of lactic acid) / 2-benzoyloxypropionic acid.

Examples of carboxylic acid anhydrides are:

Benzoic anhydride, 4-methoxybenzoic anhydride, phthalic anhydride, Sorbic anhydride, glutaric anhydride, succinic anhydride, Maleic anhydride, acetyl citric anhydride, diglycolic anhydride.

Examples of carboxamides are:
Tetrabenzoylglucoluril.

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Furthermore, instead of the percarboxylic acid itself, pure or mixed diacyl peroxides, such as benzoyl peroxide, p-tert.-butylbenzoyl peroxide, 4-methoxybonzoyl peroxide used v / earth, which decompose hydrolytically into percarboxylic acid and carboxylic acid.

The percarboxylic acids according to the invention or the substances from which the percarboxylic acids are formed when dissolving, the alcoholic solutions in solid or liquid form be admitted. Suitable solid substances are powders, granulates, tablets or other shaped solids.

The alcoholic disinfectants according to the invention can In addition to alcohols, percarboxylic acids and water, they contain other substances such as those found in commercial products can be used to improve their application properties and / or their antimicrobial effectiveness. Examples of such additives are:

Wetting agents, detergent substances, refatting agents, corrosion inhibitors, Fragrances, antimicrobial agents, colorants, pH -Corrections.

The alcoholic disinfectants according to the invention can also contain substances that act as destabilizers for the added percarboxylic acids. With the help of these destabilizers it can be achieved that the percarboxylic acids are only stable for a limited time in the alcoholic solution, e.g. only until the vegetative forms of the microorganisms and their spores have been killed. Then the percarbon

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acids in the presence of the destabilizers in them underlying carboxylic acids and oxygen, which is captured in an oxidation reaction, for example. As destabilizers e.g. aldehydes, amines, heavy metal salts are suitable.

Among the alcoholic solutions according to the invention are understood such solutions that using 10 to 100%, preferably 20 to 80% and in particular 45% Alcohol as a solvent were produced.

The term "alcohol" as used herein encompasses primary, secondary and tertiary, monohydric, dihydric and trihydric alcohols with a total carbon number of 1 to 4. The alcohols can be present as mixtures or as pure substances. Examples are: methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, tert-butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin. Preferred ethanol, i-propanol and n-propanol or mixtures of these alcohols.

The following examples illustrate the invention.

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example 1

4-Methoxyperbenzoic acid became an alcoholic solution

manufactured:

1.0 g 4-methoxyperbenzoic acid (87.5%) to 1000.0 g i-propanol (45%)

The clear colorless solution obtained was stored at room temperature and checked for its 4-methoxyperbenzoic acid content examined:

4-methoxyperbenzoic acid content (iodonetric) time content

30 ' 0.087% 90 ' 0.087% 3 ^d 0.074% 11 ^d 0.054% 13 ^d 0.034% 32 ^d 0.01%

Example 2

An alcoholic solution was made as follows:

1

4-methoxyperbenzoic acid 87.5% 0.1 0.2 0.3 0.4 non-ionic wetting agent 0.1 0.1 0.1 0.1

i-Propanol 4 5% ad 100 ad 100 ad 100 ad

and after 2 and 22 days examined for their 4-methoxyperbenzoic acid content:

4-methoxyperbenzoic acid content (iodonetric)

2 ^d 22 ^d 1 0.049% 0.022% 2 0.102% 0.042% 3 0.151% 0.062% 4th 0.195% 0.084%

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Example 3

100 g of 80% ethanol were mixed with 1 ml of a spore suspension (B. subtilis, initial germ count 6 K) / ml). Then, 0.1 g of 4-Methoxyperbenzoesäure (54 ¹ SIG) was added thereto.

According to the guidelines for testing chemical disinfectants (DGHM) the number of germs was determined as a function of time. The solution was stored at room temperature.

Time germ count / ml

2 ^h 5 χ 10 ³

3 ^h 8 χ 10 ²

4 ^h 3 χ 10 ²

5 ^h 7 χ 10 ¹ 24 ^h
48 ^h

In a comparison sample without the addition of 4-methoxyperbenzoic acid, the same number of germs as at the beginning became after 48 hours of the attempt found.

Example 4

The following ingredients were mixed:

10 TIe of ethanol

15 TIe n-propanol

20 TIe i-propanol

0.2 TIe corrosion protection (e.g. benzotriazole)

0.2 TIe wetting agent (e.g. fatty alcohol polyglycol ether)

ad 100 TIe water, perm.

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After adding 0.2 parts of peranisic acid to the solution prepared in this way, a surface disinfectant with a broad Range of effects.

Example 5

30 Tie Ethanol

50 TIe i-propanol

0.3 TIe of sodium nitrite

ad 100 TIe water, perm.

resulted in a solution which, shortly before filling into spray cans, contained 0.2 parts of peranisic acid and 0.1 part of 40% glyoxal (as a destabilizer) is added. Difluorodichloromethane is used as the propellant gas, C0 ~ or nitrogen. The weight ratio of active ingredient solution to propellant gas is 3: 1. The product is sold as a auto-sterile alcoholic spray used.

sch: cm

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Claims (5)

"25067 Claims Alcoholic disinfectants with a sporicidal effect, characterized in that they an aromatic monopercarboxylic acid of the general formula COOOH C) in which R is in the o-, m- or p-position to the percarboxylic acid group and is hydrogen, halogen, a straight-chain or branched alkyl radical having 1 to 4 carbon atoms, -OH, -OR ¹ , trifluoromethyl-, -SO ₃ II, -COOII , -COOR ¹ , -SO ₂ R ¹ or a phenyl radical, where R. is a straight or branched alkyl radical with 1 to 4 carbon atoms, or II persorbic acid, perglutaric acid, succinic acid, permaleic acid, Perlactic acid, percitric acid, peracetylcitric acid, Permethoxyacetic acid, perethoxyacetic acid or perdiglycolic acid or mixtures of these acids in alcoholic or aqueous alcoholic Solution included. 2. Disinfectant according to claim 1, characterized in that that they have the percarboxylic acid (s) dissolved in 1- to 3-hydric alcohols with 1 to 4 carbon atoms or mixtures 809850/0205 these contain alcohols with water. 3. Disinfectant according to claim 1 and 2, characterized in that the alcohols make up 10 to 100 "β of the Lösunqsinit te Ls. 4. Disinfectant according to claim 1 to 3, characterized in that that they also contain HO. 5. Disinfectant according to claim 1 to 3, characterized in that that they also have a destabilization L for which contain percarboxylic acid. 809850/0205