FI63222B - LAGRINGSTABILT KONCENTRAT FOER FRAMSTAELLNING OCH KOMPLETTERING AV FUNKTIONELLA MEDEL - Google Patents

Description

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Patent moddelat - / (si) icv.ik.Va3 C 07 C 179/10, A> 01 If 37/16 FINLAND —FINLAND (21) Pw * nulhak «« nMi - PK «MaiM6iminf 762128 (22) H» k « mlipllvl - Amöfcnlnpdkg 26.07.76 (23) AlkupiJvi — QMch «cadi <26.07 · 76 (41) Tullut Julldtuksl - Uvk offentlig 17.02.77 httmtl · i. r ^ imr« »llltu. HM »».,. * »(***.„ 'Λ,

Pa * «nt> och r * gi« tarstyr «lMn '1 Anaekta uttagd ed» utUkrftwi publkM «d · ν ± · Ό ^ (32) (33) (31) Pyydetty« Tuoikaut-Buglrd prforlMt l6.08.75 l6.08.75 »I2.OU.76 Federal Republic of Germany-Förbundsrepubliken iyskland (DE) P 2536618.1, p 2536617.0, p 26160U9.6 (71) Henkel Kommanditgesellschaft auf Aktien, Henkelstrasse 67, UOOO Diisseldorf, Federal Republic of Germany-Förbundsrepublik Grosse Bowing, Diisseldorf, Hinrich Mrozek, Dusseldorf,

Hans-Joachim Schliissler, Haan, Bernd Tinnefeld, Velbert,

Peter Vögele, Sindelfingen, Federal Republic of Germany Tyskland (DE) (7M Oy Heinänen Ab (5U) Storage-stable concentrate for the preparation and replenishment of functional substances and supplementation based on aliphatic monopercarboxylic acids.

It is already known that solutions of peracetic acid and perpropionic acid are functional substances which can be used for various purposes. They are suitable, for example, for the oxidation of organic matter in general and for the treatment of hair, straw and textiles. In particular, however, they can be used as antimicrobial and antiviral agents, in which case peracetic acid is most suitable. Pure peracids cause difficulties not only during manufacture but also due to the risk of fire and explosion, which makes them difficult to handle. Therefore, in practice, the acids are not used in pure form but as a mixture of, for example, 34-45% peracetic acid and 40-35% acetic acid. The proportion of water is usually less than 15 percent. The disadvantage of these concentrates is that, due to their pungent odor and corrosive effect, the user, who must first dilute the concentrates, can only handle them in compliance with the strict safety regulations. If, on the other hand, concentrates are prepared which contain, for example, 5 to 25% by weight of peracetic acid alone and the rest of the water, these are not storage stable.

The object of the present invention is to provide a storage-stable concentrate for the preparation and replenishment of functional substances based on aliphatic monoper carboxylic acids, in which the above-mentioned drawbacks have been avoided. The invention is characterized in that the concentrate contains 0.5 to 20% by weight of peracetic acid and / or acetic acid or perpropionic acid and / or propionic acid, 25 to 40% by weight of optionally phosphonic acid or its water-soluble salts, optionally an anionic wetting agent and the remainder of water.

Most preferably, the storage-stable concentrate according to the invention contains 5 to 10% by weight of peracetic acid and / or acetic acid.

The preparation of the concentrate according to the invention can be carried out in a simple manner by mixing a solution of H 2 O 2, preferably at a concentration of about 33% by weight, with peracetic acid and optionally acetic acid. It is also suitable to prepare the mixture only by adding a concentrated solution of acetic acid with a corresponding amount of acetic acid. Since the products are usually not delivered directly to the user but first stored, the concentration of peracetic acid is adjusted. The formation of peracetic acid can be accelerated catalytically with a small amount of mineral acid (0.1-1% by weight However, such an increase is generally not necessary for the reasons set out above.

Such concentrates prepared, for example, from 30% H2O2. 5% acetic acid and 65% water, do not have an annoying odor and are easy to handle, i.e. they can be easily diluted in food technology and the pharmaceutical sector to normal use concentrations of 0.1-1% without the need for substantial precautions.

It has further been found that concentrates are obtained for the preparation of antimicrobials having increased efficacy based on the above components, provided that they additionally contain 0.25 to 10% by weight of phosphonic acid or their acid salts.

3,63222

By phosphonic acids according to the invention are meant those which have the ability to complex divalent metal cations, in particular calcium. Thus, a large number of phosphonic acids are possible, which, in addition to the phosphonic acid groups, may possibly also contain carboxyl groups. Suitable phosphonic acids are those compounds of formula!

HgO 2 P - C - PO 2 H 2 (H) (1) wherein = phenyl group, cyclo- 2 alkyl group or alkyl group having 1 to 6 carbon atoms, R 2 and R 4 = R 2 = hydrogen atom or alkyl group,

HgO ^ P - C - PO ^ Hg (II) having 1 to 4 carbon atoms,

OF

R 2 r 3 or compounds such as amininotrimethylenephosphonic acid, dimethylaminoethane diphosphonic acid, aminoacetic acid NN-dimethylenephosphonic acid, ethylenediamine tetramethylene phosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 2-diphosphonic acid, phosphonomer succinic acid and 1-phosphono-1-methyl succinic acid.

Particularly suitable are: dimethylaminomethanediphosphonic acid, 1-dmino-1-phenylmethanediphosphonic acid, amininotrimethylenephosphonic acid, aminoacetic acid N-N-dimethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid.

Instead of the phosphonic acids described above, their acidic water-soluble salts can also be used, in particular the sodium, potassium, ammonium or alkanolamine salts. If desired, mixtures of different phosphonic acids or their acid salts can also be used.

In the wide range of uses of the functional substances described above, for example for the oxidation of organic materials in general or for the treatment of hair, straw and textiles and as microbicides and viruses, it is in many cases advantageous to use them in combination with wetting agents to improve the desired properties.

According to the invention, it has been found that storage-stable concentrates of the type described above can be obtained if anionic wetting agents in the form of alkylbenzenesulfonates, alkyl sulphates and / or alkyl sulfonates of 0.05 to 5% by weight are also added.

Suitable alkylbenzene sulfonates are those which contain an alkyl group having 6 to 18 carbon atoms, preferably 9 to 15 carbon atoms. Instead of alkylbenzenesulfonates, alkyl sulphates or alkyl sulfonates having an alkyl group having a chain length of 12 to 18 carbon atoms are also suitable. Of course, mixtures of the anionic wetting agents presented can also be used, if desired.

It has been shown that the additions shown remain stable in the concentrates also for long periods of time and thus the concentration of peracetic acid also remains constant in the concentrate. If, on the other hand, soaps or ordinary non-ionic wetting agents are used as wetting agents, sufficient stability will not be achieved.

The new storage-stable concentrates of the described functional substances can be used for all purposes for which a wetting and oxidizing effect must be obtained and in which the disadvantages of the previously known pure peracids have made it difficult or impossible to use them. The substances still have the advantage that they are suitable for standing disinfection to prevent secondary microbial growth in machines, which is particularly desirable in the food industry after cleaning. In addition, due to the Og content, there is a long-term effect against most microorganisms.

The pH of the working solution is constantly weakly acidic, and the acetic acid waste after disinfection is very small, which makes the substances also suitable for disinfection where rinsing is no longer required.

Example 1

Prepare a concentrate for the preparation of microbicidal substances by mixing 63222 5 5% by weight of acetic acid 30% by weight of H 2 O 2 65% by weight of water

The concentrate was stored and sampled at regular intervals to determine H 2 O 2 - and peracetic acid content. The results are shown in the following Table 1. For comparison, a concentrate containing 8% by weight of peracetic acid, 8.5% by weight of acetic acid, 1% by weight of H 2 O 2 and 82.5% by weight of water was further prepared. This mixture was sampled at regular intervals and the peracetic acid content was determined. The results are shown in Table 2. It is clear that the substances are not stable.

Table 1 _Time__HpC 2% Peracetic acid percentage 1 week 28.5 3.3 1 month 28.3 3.5 3 months 28.3 3.5 Å. .

6 months 28.2 3.5

Jl ------ ---------- 1

Table 2 _ Time_____Weight weight peracid 1 h 7.6 10 h 6.1 2 days 3.0 j H days 1.2 I 1 month_ 0.6

Example 2 63222 6

By performing a suspension test according to the instructions of the DGHM, the killing time of Stafylokockus aureus was determined by means of mixtures of small amounts of acetic acid or propionic acid, respectively. The results are shown in Table 3 below.

Table 3 'ppm H 2 O 2 [ΪΪ65 1165 1165 ~ "' ppm acetic acid 50 i j ppm propionic acid 50 | killing time (min) 20 5 5

Example 3

A concentrate was prepared with 33 wt% HgOg »5 wt% acetic acid, 0.5 wt% phosphonic acid and the rest water.

The following phosphonic acids were added to the various concentrates.

A) Dimethylaminoethanediphosphonic acid B) 1-Amino-1-phenylmethanediphosphonic acid C) Aminotrimethylenephosphonic acid D) Aminoacetic acid-NN-dimethylenephosphonic acid E) 1-Hydroxyethane-1,1-diphosphonic acid P) 1-Amino-1-cyclohexyl-1,1-cyclohexyl 1-N-methylaminoethane-1,1-diphosphonic acid H) ethylenediamine-tetramethylenephosphonic acid.

In addition, a concentrate without phosphonic acid was prepared to obtain a reference value.

The concentrates were stored for a period of time and diluted to a concentration of 0.1%. The efficacy of the microbicide was tested in a suspension experiment according to the instructions die Deutsche Gesellscheft fiir Hygiene und Mikrobiologie (DGHM). Stafylokockos aureus and Escheria keel were used as sample strains.

The observed killing times in minutes are shown in Table 4 below.

7

Table 4 63222

Increase Killing time in minutes

Staf. aureus E. keel none 10 60 A 1 10 B 1 10 C 1 20 D 1 20 E 1 20 P 5 40 G 5 40 H 5 40 J - - - - ..... _ |

Example .4

Storage-stable concentrates were prepared with 33% 5% acetic acid, 3% phosphoric acid, 1-hydroxyethane-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-dicarboxylic acid, respectively. The concentrates were stored for ψ 8 days and then diluted to a working concentration of 0.05%.

Microbicide efficacy was determined by microbial reduction "D". The following test procedure was used: o 0.1 ml / ml of microbial suspension (microbial count 10 / ml) was added to 10 ml of disinfectant solution (corresponding to a control value of 10 ml of water), the mixture was stirred for 5 minutes, 0.1 ml was removed and added to 10 ml of release solution (Enthemmung). 0.5% aqueous thiosulfate solution). After 15 minutes, the microbial count of this solution was determined according to the Koch plate method.

The evaluation was performed according to the following formula.

the germination number of the control sample V = log - the germination number D of the disinfectant solution thus quantitatively indicates the germination reduction (Keimreduktion) in locar rhythmic form, for example D = 1 means that the germination number 8 63222 decreased by ten power.

The reference value with the addition of phosphoric acid shows that the effect of the different acidity of the acidity level in the added phosphonic acid is not decisive (see Table 5).

Table 5 *. D-value! E-koli Pseudomonas Percentage increase in aeruginosa _________ 0.5 2.0 1) 0.4 2.3 3) phosphoric acid 0.5 2.5 5) __ 3.0 over 4.8 1) 2.2 over 4.8 3 ) 1-hydroxyethane- more than 5.3 more than 4.8 5) M-alphosphonic acid I .........

0.9 I 3.5 1) 1.0 l more than 4.8 3) 2-phosphonibutane-1,2-i more than 4.9 i 4.8__s) 4-tricarboxylic acid ......

Note: "over" before the D value means that all microbes have been killed.

Example 5

The concentrate was prepared by mixing together 5% by weight of acetic acid, 27.6% by weight of H2O2, 1% by weight of alkyl (C2-2 * Cyg sulfonate) and 66.4% by weight of water.

The concentrate was allowed to stand and a sample was taken at certain intervals to determine the HgOg and peracetic acid content. The results are shown in Table 6 below.

9

Table 6 ____ to 63222

Stability of mixtures on addition of alkyl sulphonate ~~ 2 ~ 0 ° C ~ Time | ____1

Percent H20p Percent peracetic acid _______________ ___i acid____________ Initial value 26.2 2.3 1 month 26.1 2.3 3 months 25.1 2.3 6 months 25.0 2.4 j Practically the same results were obtained when using concentrates, which contained 1? δ alkyl sulphate instead of 1 i »alkyl sulphonate.

Example 6

A concentrate for the preparation of microbicidal agents was prepared by mixing together 5% by weight of acetic acid, 27.6% by weight of HgOg, 1.5% by weight of hydroxyethane-1,1-diphosphonic acid, 1.5% by weight of alkyl (C 2) -benzenesulfonate and 64.4% by weight of water.

The concentrate was divided into two halves and stored at 20 and 40 ° C, respectively, at which time samples were taken at regular intervals to determine the H 2 O 2 and peracetic acid content. The results are shown in the following Table 7. It is clear that the concentrate remained stable for a long time even in the presence of said wetting agent.

Table 7 63222 10

Hydrogen peroxide and peracetic acid content at 20 and 40 ° C, respectively.

! Temperature Time Percent Percent peretika-! acid; 20 ° C Starting value 28.3 2.3 • 8 days 28.1 2.3 i 1 month 27.5 2.3 | 3 months 27.3 2.3 i 6 months 26.5 2.3 40 ° C Starting value 28.2 2.2 8 days 27.8 2.2 1 month 26.8 2.2 '3 months 26.7 2 , 2

Claims (5)

Storage-stable concentrate for the preparation and replenishment of functional substances based on aliphatic monopercarboxylic acids, characterized in that the concentrate contains 0.5 to 20% by weight of peracetic acid and / or acetic acid or perpropionic acid and / or propionic acid, optionally 25 to 40% by weight water-soluble salts, possibly an anionic wetting agent, and the rest of the water. Storage-stable concentrate according to Claim 1, characterized in that the concentrate contains 5 to 10% by weight of peracetic acid and / or acetic acid. Storage-stable concentrate according to Claim 1 or 2, characterized in that the concentrate contains 0.25 to 10% by weight of phosphonic acid or its water-soluble salts. Storage-stable concentrate according to Claim 3, characterized in that the concentrate contains, as a phosphonic acid, one of the following compounds: mixtures. Storage-stable concentrate according to one of Claims 1 to 4, characterized in that the concentrate contains 0.05 to 5% by weight of anionic wetting agent in the form of an alkyl benzene sulfonate, an alkyl sulphate and / or an alkyl sulfonate.