DK156026B - DIFFICULT, STORAGE-STABLE CONCENTRATES BASED ON MONOPERIC CARBOXYL ACIDS - Google Patents

Description

DK 156026B

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to aqueous, storage stable concentrates of microbicidal and oxidizing mixtures based on peracetic or perpropionic acid and H 2 O 2. It is known that solutions of peracetic and perpropionic acids are functional agents which can be used for various purposes. They are suitable, for example, for the oxidation of organic matter in general heat and for the treatment of hair, straw and textiles. In particular, they can be used as microbicidal and virucidal agents. Preferably, peracetic acid is used.

However, the pure peracids are not only problematic in their preparation but also difficult to handle due to the associated fire and explosion risk. Therefore, in practice, the 15 acids are not used in pure form, but in mixtures of, for example, 35 to 5% peracetic acid and 40 to 55% acetic acid. The water content is generally below 15% · The disadvantage of these concentrates is that, due to their stinging odor and their corrosive effect, they can only be handled by the consumer, who initially has to dilute the concentrates, 20 under strict safety rules. On the other hand, if concentrates of, for example, 5 to 25% by weight of peracid are produced alone and the remainder of water, these concentrates are not storage stable.

It has now been found that the above-mentioned drawbacks can be avoided and further enhanced microbiocidal action can be obtained with aqueous, storage stable concentrates according to the invention on the basis of aliphatic monopercarboxylic acids, when characterized by a content of 0.5 to 20% by weight peracid. with 2 to 3 carbon atoms and / or the corresponding aliphatic monocarboxylic acids and 30 to 40% by weight H2O2, 0.25-10% by weight phosphonic acid or acidic water-soluble salts thereof, water and optionally wetting agents.

Preferably, the storage stable H2 O2 containing concentrates are characterized by a content of 5 to 10% by weight peracetic acid and / or acetic acid as well as a molar excess of H2 O2 relative to peracid, the latter calculated as monocarboxylic acid, of at least 2: 1. , preferably 3: 1 to 50: 1. The preparation is carried out in a simple manner by mixing: of H preferably with a concentration reaching ca.

2

DK 156026 B

33% by weight, with peracetic acid and optionally acetic acid. Advantageously, the mixtures can also be prepared by adding only the corresponding amount of acetic acid to the concentrated H 2 C 2 solution. As the products are mostly not delivered directly for consumption, but first stored, a similar content of acetic acid is obtained. The peracetic acid formation can, if desired, be catalytically accelerated by a small amount of mineral acid (0.1 to 1%). Generally, however, such an addition is not necessary for the above reasons.

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Concentrates, for example, made from 30% H2O2, 5% acetic acid and 65% water, no longer have any troublesome odors and are easy to handle, ie they can be easily diluted to those of the food technology and medical industry usual application concentrations from 0.1 to 1% without requiring significant safety measures.

According to the invention, it has been found that concentrates are obtained for the preparation of microbicidal agents with increased effect when, in addition to the indicated amounts of peracid and H 2 O 2, they further contain 0.25 to 10% by weight phosphonic acid or acid salts thereof.

Phosphonic acids within the meaning of the present invention are to be understood as those capable of complexly binding the divalent metal cations, especially calcium. Thus, a greater number of phosphonic acids are considered which, in addition to the phosphonic acid groups, may also contain carboxyl groups. Suitable phosphonic acids are thus compounds of formulas 30 R1. in H₂O ^P - C --PO₂ H2 (I) wherein R = a phenyl group, an OH cycloalkyl group or an alkyl = group of 1-6 carbon atoms, and R and R ^ = hydrogen atoms or alkyl groups of 1-4 carbon atoms t H2 ° 3p - $ - PO3H2 (II)

4 V

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DK 156026 B

or compounds such as aminotrimethylene phosphonic acid, dimethylaminomethane diphosphonic acid, aminoacetic acid NN-dimethylene phosphonic acid, ethylenediamine-1-tetramethylene-phosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 2-phosphonic butane acid, 2,4-phosphonic acid, 1,2,4 1-phosphono-l-methylsuccinic.

In particular, consideration is given to: 15 dimethylaminomethane diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, aminotrimethylene phosphonic acid, aminoacetic acid N-N-dimethylene phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid.

Instead of the listed phosphonic acids, their acidic water-soluble salts may also be used, such as, for example, sodium, potassium, ammonium or alkanolamine salts. If desired, mixtures of the individual phosphonic acids or their acidic salts may also be used.

2 5

In the many applications of the above-described functional agents, for example, for the oxidation of organic matter «in general or for the treatment of hair, straw and textiles, as well as as microbicidal and virucidal agents, it is in many cases advantageous to use them while simultaneously adding a wetting agent to further enhance the desired properties.

It has been found that particular storage stable concentrates of the kind described above are obtained when adding anion-active wetting agents selected from alkylbenzenesulfonate, alkylsulfate and / or alkylsulfonate in amounts of 0.05 to 5% by weight.

As alkyl benzene sulfonates, those containing an alkyl group having 6 to 18 carbon atoms are considered, preferably 9 to 1 C ^ a a. "AX a." Μ a -a T aX a J aX X * a aa a "7 AMn am a * i ”7 <Pavi λ" γ- λ νινί a IrArwmA ν »ΛΛΌη 4

DK 156026 B

alkyl sulfates or alkyl sulfonates having an alkyl group having the chain length 12 to 18 carbon atoms in consideration. Of course, if desired, mixtures of the aforementioned anionic wetting agents can also be used.

It has been found that the said additives also remain stable in the concentrates for a long period of time and that the content of peracetic acid thus also remains constant in the concentrate. By contrast, if softener additives are used as soaps or the usual nonionic wetting agents, a sufficient stability is not achieved.

The present storage stable concentrates of the described functional agents can be used for all purposes for which a wetting and oxidizing effect is to be obtained, and where the disadvantages of the known pure peracid per 1 s make or exclude its use. Furthermore, the agents also have the advantage of being suitable for disinfection in order to prevent a secondary germination on machines after cleaning, especially in the food industry.

Moreover, due to their content of HPOP, a long-term effect on most microorganisms occurs.

Furthermore, the pH of the solution of use is slightly acidic and the acetic acid residue after the disinfections is extremely low, so that the agents are also suitable for a disinfection in which a rinsing is no longer necessary.

2 5

The following examples illustrate the invention,

Example 1.

A concentrate was prepared to prepare microbicidal agents by mixing 1 wt.% Acetic acid 30 wt.

35

The concentrate was allowed to stand and for a certain time a sample was taken to determine the content of H 2 O 2 and peracetic acid. The results are set forth in the following Table 1. For comparison, an additional concentrate containing 8 weight was prepared

DK 156026B

5 peracetic acid, 8.5 wt.% Acetic acid, 1 wt.% H2O2 and 82.5 wt.% Water. Samples were taken from the mixture after a certain period of time and the peracetic acid content was determined. The results are given in Table 2. It is clear that the latter agent is not stable 5

Table 1.

Time% Peracetic acid% 10 1 week 28.5 3.3 1 month 28.5 3.5 3 months 28.3 3.5 6 months 28.2 3.5 15

Table 2.

Time__ Weight% persvre 1 h 7.6 20 10 h 6.1 2 days 3.0 14 days 1.2 1 month 0.6 25 Example 2,.

Concentrates of 33% by weight 5% by weight of acetic acid, 0.5% by weight of phosphonic acid and the remainder of water were prepared.

The individual concentrates were added to the following phosphonic acids.

A) dimethylaminomethane diphosphonic acid B) 1-amino-1-phenylmethane diphosphonic acid C) aminotrimethylene phosphonic acid D) aminoacetic acid NN-dimethylene phosphonic acid E) 1-hydroxyethane-1,1-diphosphonic acid F) 1-amino-1-cyclohexyl-1,1-diplophosphonic acid ) 1-N-Methylaminoethane-1,1-diphosphonic acid H ^ eflyl pnri in ami n-hpf '.- rounAffhyl pri— ^ hnffTVhrmsvr'A.

6

DK 156026 B

To obtain a comparative value, no additional phosphonic acid was added to an additional concentrate.

5

The concentrates were left until equilibrium was established between HgO4 and acetic or peracetic acid, and then diluted to a concentration of 0.1%. The equilibrium adjustment is catalytically accelerated by phosphonic acid in the concentrate, cf. section 3 on page 2. Suspension experiments on microbicidal action were carried out in accordance with the guidelines laid down by the German company for hygiene and microbiology (DGHM). Staphylococus avreus and Escheria coli were used as test strains.

15

The extinction times found in minutes are listed in the following Table 3.

Table 3 '.

20 _ ______

Addition Extinction times in minutes

Staph, aureus E. coli without 10 60 A 1 10 25 B 1 10 C 1 20 D 1 20 E 1 20 F 5 40 30 G 5 40 H 5 40

Example 3

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Storage stable concentrates were prepared from 33% & 2® 2 '5% acetic acid, 3% phosphoric acid or 1-hydroxyethane-1,1-diphosphonic acid or 2-phosphonobutane-1,2,4-dicarboxylic acid. The concentrates were left for 8 days and then diluted to an application concentrate.

DK 156026 B

T

The microbicidal effect was determined by the germ reduction "D". The following test method was used:

ISLAND

5 0.1 ml of a seed suspension (seed count 10 / ml) is added to 10 ml of disinfection solution (or as control value to 10 ml of water), the mixture is stirred for 5 minutes and 0.1 ml is taken out and added to 10 ml of inhibition solution (0.5% aqueous thiosulfate solution). Of this, the seed count was determined after 15 minutes according to the Kochske plac 1 ° process.

The assessment is carried out according to the formula for germinal control imt germs of all the infections solved 15 D thus indicates the germ reduction quantitatively in logerithmic form, ie <D = 1 means that the germ number was reduced by a tier potency.

The comparison value with the addition of phosphoric acid shows that the influence of the acidity of the added phosphonic acids is not decisive (see Table 4).

Table 4.

25 D-value E-coli Pseudomonas% addition aeruginosa 0.5 2.0 1) 30 0.4 2.3 3) Hiosphoric acid 0.5 2.5__5 _ 3.0 above 4.8 1) 1-hydroxyethane-1, 1- 2.2 over 4.8 3 seconds diphosphonic acid over 5.3 over 4.8 5) 3.5 1) 2-phosphonobutane-1,2,4-1,0 over 4.8 3 tricarboxylic acid over 4.9 over 4.8 5) 8

DK 156026 B

Note: The "above" before the D value means that all germs are eradicated.

Example 4.

A concentrate was prepared by mixing 5 wt.% In acetic acid 10 27.6 wt.% H 2 O 2 1 wt.% Alkyl (C C --C ^ g sulfonate) and 66.4 wt.% Water.

The concentrate was left to stand and after a certain time a sample was taken to determine the content of H 2 O 2 and peracetic acid. The results are given in the following Table 5.

Table 5. Stability of mixtures with addition of an alkyl sulfonate 20 20 ° C Time% H 2 O 2% peracetic acid initial value 26.2 2.3 1 month 26.1 2.3 25 3 months 25.1 2.3 6 months 25.0 2 , 3 'Λ

Practically the same results are obtained when the concentrates instead of 1% alkyl sulfonate contain 1% alkyl sulfate.

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Example 5

A concentrate was prepared for preparing microbicidal agents by mixing 35% by weight acetic acid 27.6% by weight H2 O2 1.5% by weight hydroxyethane-1,1-diphosphonic acid 1.5% by weight alkyl (C-, O) -benzensulphonate and 9

DK 156026 B

The concentrate was divided into two halves, which were left at 20 ° C and 40 ° C, respectively, and after a certain period samples were taken to determine the content of and peracetic acid. The results are given in the following table 6. It is clear that the concentrates are also stable over a longer period of time in the presence of the wetting agents mentioned.

10 15 20 25 30 35

DK 156026 B

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Claims (4)

Aqueous storage stable concentrates based on aliphatic C monopercarboxylic acids, characterized in that they contain 0.5 to 20% by weight peracid with 2 to 3 carbon atoms and / or the corresponding aliphatic monocarboxylic acids, 25 to 40% by weight H2O2, 0.25-10% by weight of phosphonic acid or acidic water-soluble salts thereof and water and optionally wetting agents. 10 Concentrates according to claim 1, characterized in that they contain 5 to 10% by weight peracetic acid and / or acetic acid and a molar excess of H2O2 relative to peracid, the latter being calculated as monocarboxylic acid, of at least 2: 1, 15 preferably 3: 1 to 50: 1. Concentrates according to claim 1 or 2, characterized in that, as phosphonic acid, they contain one of the following compounds 20 di methyl amine nornethand in phosphonic acid 1-am in no-1-phenyl methaned iphosphonic acid ami notrimethylene phosphonic acid ami acetic acid NN-dimethylphosphonic acid 25 1-hydroxyethane-1,1-diphosphonic acid or acidic water-soluble salts thereof or mixtures thereof. Concentrates according to any one of claims 1 to 3, characterized in that they contain 0.05 to 5% by weight of anion-active wetting agent selected from alkybenzenesulfonate, alkyl sulfate and / or alkyl sulfonate. 35