JPS6332326B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water-based disinfectant based on H ₂ O ₂ and its use. Water, which until recently was an abundant and cheap natural substance, has gradually become - especially for industry - a valuable and expensive "operating material" and is no longer present in arbitrary quantities. Therefore, in recent times, both in municipal areas and in industry, efforts have been made to limit the use of fresh water as much as possible and to purify and reuse the used water, i.e. - possibly by linking one-stage or multi-stage regeneration processes. -Efforts are being made to recycle. Typical examples are cold water circulation in various industrial sectors and circulation equipment in bathing areas. An example is the closed circulation system in a paper mill.
There, the water separated mechanically, for example by filtration or pressing, is used again. The used water that is guided through the circulation path generally contains many impurities that serve as nutrients for all kinds of microorganisms. In the case of paper mills, the pulp present in the very filtered or pressed water provides a very good culture medium for algae, fungi and other bacteria, which can hardly be prevented from entering even closed water systems. The growth of these bacteria results in slime formation or mold development, which can cause significant damage or obstruction at various locations in the circulatory system. It is known that the development of all types of microorganisms in water can be inhibited as fully as possible by the addition of suitable disinfectants. It is also known that for that purpose one should use fungicides which are effective without leaving any products of the same addition, or at least without leaving any harmful or toxic or corrosion-promoting substances. One such known disinfectant that is completely consumed without forming any residue is hydrogen peroxide, which decomposes in oxygen and water. Hydrogen peroxide not only has sterilizing, deodorizing, oxidizing and anti-inflammatory effects, but also has anti-fouling and killing effects (Dermatologische
(Wochenschrift) 1966, Vol. 152, p. 1105). However, hydrogen peroxide cannot be used universally as a disinfectant, and is particularly unsuitable for the continuous treatment of certain used waters. This is because various microorganisms can form within a relatively short time resistance bodies which can no longer be attacked by H ₂ O ₂ . West German Patent Publication No. 2228011 describes a biological purification method that satisfies the oxygen demand necessary for total aerobic bacterial purification and at the same time prevents the growth of filamentous fungi. amount of H ₂ O ₂ is mixed with the wastewater. In other words, this method utilizes the selective effect of H ₂ O ₂ to completely exterminate certain microorganisms, while at the same time optimizing the growth conditions for other microorganisms. It has therefore already been proposed to use hydrogen peroxide together with organic compounds as disinfectants in order to make aqueous systems completely sterile. For example, German Patent Application No. 2221047 describes a method for preparing a cleaning and disinfecting solution for soft contact lenses, in which hydrogen peroxide or a non-toxic water-soluble peroxide is mixed with phenylmercury (). It is used in the form of an isotonic aqueous solution together with its salts, especially sodium methylmercury thiosalicylate. However, this known agent is also not universally usable, especially due to the toxicity of mercury. This toxicity not only prohibits the use of the same agent in bathing facilities, but also in industry, for example in the paper industry for producing paper for food packaging or in the pharmaceutical industry, or in humans in cases of damage to the circulatory system. Their use is also prohibited in other areas where the substances used by them may come into contact with toxic substances. Therefore, another disinfectant with a broader range of effectiveness than hydrogen peroxide alone was needed. The object of the present invention is to satisfy this requirement, to be universally usable, to effectively exterminate all types of bacteria, to leave no harmful or corrosive products behind, to be non-toxic and non-toxic. An object of the present invention is to provide a water-based disinfectant based on H ₂ O ₂ that does not generate decomposition products. This task is achieved according to the invention by using 8-hydroxyquinoline, dipicolinic acid and/or the general formula:
R ₂ NSO ₃ H [wherein, R is a hydrogen atom or 1 C atom]
The problem is solved by fungicides of the type mentioned at the outset, which contain amidosulfonic acids or salts thereof representing ~6 alkyl groups] and optionally corrosion inhibitors. It has surprisingly been found that the agents according to the invention have a synergistic effect. That is, the joint effect of both components, hydrogen peroxide and the aromatic compound and/or amidosulfonic acid, is stronger than the simple sum of the effects of each component of the same composition. The essential advantage of the agent according to the invention in practical use is that the stability of the hydrogen peroxide is not adversely affected by one or more fungicidal additives.
That is, the storage stability of the disinfectant and therefore the economics of its use are not reduced. A further essential advantage of the agent according to the invention is that the substances remaining after water treatment and which, unlike H ₂ O ₂ itself, are completely consumed by chemical reactions are practically physiologically unfriendly to human organs. It is not having a property. This is of particular importance for the use of the agents according to the invention for the disinfection of pool water or - in industry - in paper mills producing packaging materials for food packaging. One advantageous embodiment of the agent according to the invention is 1
It contains the synergistically active substance or substances in the form of an aqueous, optionally inorganic acidic solution. The addition of small amounts of inorganic acids has the advantage that the optionally contained active substances with relatively low water solubility can be easily dissolved. A further advantageous form of implementation of the active agent according to the invention provides that one or more synergistic active substances are combined at 0.1
8-hydroxyquinoline and/or in an amount of ~5% by weight
Or a fungicide containing dipicolinic acid. The disinfectant according to the invention contains hydrogen peroxide, preferably in the form of a commercially available, optionally stabilized, aqueous solution. Conventional H ₂ O ₂ stabilizers such as sodium pyrophosphate do not adversely affect the synergistic effect of the agents of the invention nor the properties of the components contained in the agents of the invention. The problem of the present invention mentioned at the beginning is that 35% H ₂ O ₂
This problem is solved by using the fungicide according to the invention at a concentration corresponding to 0.01 to 2 ml of aqueous solution/medium to be treated. If the pipeline system contains parts that are susceptible to corrosion or are exposed to the risk of corrosion, such as pipe fittings, pumps, connections of any kind, the disinfectant according to the invention may optionally be supplemented with a corrosion inhibitor. For example, ammonium nitrate can be added without reducing the synergistic effect between hydrogen peroxide and the organic compound. The addition of the active agent according to the invention to the aqueous medium to be sterilized is carried out using conventional equipment, for example continuous or batch-operated dosing equipment made of materials that are not attacked by hydrogen peroxide. The invention will be explained in more detail by examples and experimental records below. Examples 1-5 below are effective fungicides according to the present invention. They are produced by mixing a 35% strength by weight aqueous hydrogen peroxide solution with the synergistic effect-enhancing agents mentioned in the respective stated proportions and can be stored in this form without problems without losing their effectiveness. It can be used at any time after production. Example 1 H ₂ O ₂ 35% by weight Ammonium amidosulfonate 2% by weight Water Example of residual amount 2 H ₂ O ₂ 35% by weight Dipicolinic acid 0.5% by weight Water Example of residual amount 3 H ₂ O ₂ 35% by weight Ammonium amidosulfonate 2 Weight% Sodium pyrophosphate 0.5g/Water Example of residual amount 4 H ₂ O ₂ 35% by weight Ammonium amidosulfonate 2% by weight Dipicolinic acid 0.25% by weight Water Example of residual amount 5 H ₂ O ₂ 35% by weight 8-Hydroxyquinoline 2% by weight % dipicolinic acid 0.25% by weight Sulfuric acid Amount to completely dissolve hydroxyquinoline Water Remaining amount The bactericidal efficacy of the agents according to the invention as described in Examples 1 to 5 above was determined by the following experiments. For the purpose of enriching cellulolytic substances
NaNO ₃ 0.5g, K ₂ HPO ₄ 1g, MgSO ₄・7H ₂ o0.5
Dubo's salt solution consisting of 0.5 g of KCl, 0.01 g of FeSO ₄ 7H ₂ o, and 1 g of distilled water was added to 5 g of cellulose powder, 0.1 g of yeast extract, and 5 g of humus.
and aerated for several weeks. Next, this Dubo salt solution and the enriched cellulolytic material substrate 10%
An experimental substance containing the following was produced. This experimental material was mixed with 0.25 ml/0.05 ml of the fungicide according to Examples 1 to 5.
ml/ at 15°C and slightly aerated. PC-agar (cultured at 22°C for 10 days) at the start of the experiment and 1, 7, and 14 or 20 days later.
The total number of bacteria was determined. In addition, to measure the total number of bacteria originally contained in the experimental material,
A blank test, that is, a test with a sample without added fungicide, was also conducted. For comparison and to demonstrate the synergistic effect achieved with the agent according to the invention, hydrogen peroxide is not included. Thus, _{the same} experimental materials containing only the organic components (including _Na2H2P2O7 and _H2SO4 ) described in _Examples 1-5 were tested under the _same conditions. Furthermore, for comparison, 35% by weight of the commercially supplied form
The bactericidal effect of the H ₂ O ₂ solution alone, ie without the addition of further active substances, was determined. The results of these tests are shown in Tables 1 and 2 below. The table shows the number of viable bacteria contained in 1 ml of the experimental substance (“<10 ¹ ” means that no viable bacteria were found in 0.1 ml of the experimental substance). As examples 1' to 5', examples 1 to 5'
A comparative agent was used which had the same composition as the agent according to No. 5, but only contained no H ₂ O ₂ .

【table】

【table】

[Table] From the results in Tables 1 and 2, when the disinfectant according to the present invention is used at a concentration of 0.25 ml/ml, no living bacteria were confirmed in 0. ml of the test solution one day after the start of the experiment. On the other hand, when using a 35% by weight H ₂ O ₂ solution, the number of viable bacteria was still 2 x 10 ² after 1 day, and an additional 5 x 10 ² after 14 days. In case of use of the substance alone, i.e. without addition of H ₂ O ₂ , after 1 day still 3×10 ⁵ to 2×
It is recognized that the number of viable bacteria of 10 ⁵ to 10 ⁶ could be confirmed even after 10 ⁶ and 14 days. From this fact, the effect of the agent according to the present invention is that H ₂ O ₂
This proves to be a true synergistic effect, and not just the sum of the respective effects of each added active ingredient. Furthermore, the same results show that neither the presence of customary stabilizers for H ₂ O ₂ (Example 3) nor the presence of small amounts of inorganic acids (Example 5) reduces the synergistic effect and action of the agents according to the invention. . The agent according to the invention is therefore very well suited for the disinfection and/or disinfection of water systems in general and is extremely suitable not only for the use of circulating water in industry, but also for the treatment of other areas, for example swimming pool water. It is excellent.

Claims (1)

[Scope of Claims] 1. For use in the water system of paper mills producing packaging materials for circulating industrial water and food packaging.
In slime control agents based on H ₂ O ₂ ,
This includes 8-hydroxyquinoline, dipicolinic acid as a synergistic potency-enhancing agent or a mixture of the same agents and the general formula R ₂ NSO ₃ H, where R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. A slime control agent, characterized in that it contains one or more amidosulfonic acids or salts thereof as shown below and optionally a corrosion inhibitor in an aqueous solution. 2. The slime control agent according to claim 1, which contains the synergistic efficacy-enhancing substance optionally in the form of an inorganic acidic aqueous solution. 3. The slime control agent according to claim 1 or 2, which contains one or more synergistic efficacy-enhancing substances in an amount of 0.1 to 5% by weight. 4. A slime control agent according to any one of claims 1 to 3, which contains H ₂ O ₂ in the form of a commercially available, optionally stabilized, aqueous solution. 5 35% H ₂ O ₂ - aqueous solution 0.01 per medium to be treated
The slime control agent according to any one of claims 1 to 4, which is used at a concentration corresponding to ~2 ml.