DE2349090A1 - Synergistic antimicrobial compsns. - contains an unsatd. acid and formaldehyde - Google Patents

Abstract

The parent patent described the anti-microbial action of unsatd. carboxylic acids of formula: R1-CH=CH-(CH2)n-COOH (where R1 is 5-16C alkyl, and n is 0 or 1) in acid media of pH less than 5. In this addn. is described how the disinfecting action of the above acids can be synergistically increased by using them in combination with formaldehyde. The acids are used as disinfectants in industry (dairies, breweries, food processing plant etc.), in veterinary applications (coops, pens etc.) and esp. in hospitals.

Description

Düsseldorf, September 26th, 1997? . Henkel & Gie <ambH

Henkelstrasse 67. "I '' '",' Patent Department *

Z / Br patent application

"Use of unsaturated carboxylic acids in combination with formaldehyde as an antimicrobial agent"

(Additional application to the patent

(Patent application P 23 10 246.7) (D 4576)) ;

The invention relates to the use of a synergistic Combination of unsaturated aliphatic carboxylic acids of medium to higher chain length with formaldehyde for combating of bacteria and fungi in acidic pH ranges and is a further development of the patent. ... ...

(Patent application P 2 ^ 10 246.7).

Subject of the patent. ... ... (patent application P 2j>. 10 246.7) is the use of unsaturated carboxylic acids of the general formula

R ₁ - CH = CH - ( ^CH ₂ ) _n - COOH,

in the R. an alkyl radical with 5-16 carbon atoms and η represent the numbers 0 or 1, as antimicrobial substances in acidic areas with pH values ^ 5> ·

The unsaturated carboxylic acids to be used according to the invention can be prepared in a known manner after the synthesis of Knoevenagel from corresponding longer-chain aldehydes with malonic acid, the reaction in the presence of ammonia, primary or secondary nitrogen bases to form ^, ^ - unsaturated carboxylic acids and in the presence of. tertiary nitrogen bases to cx, y0-unsaturated carboxylic acids with possibly low proportions of 5 - 10 % of ^, ^ - unsaturated carboxylic acids. Corresponding information on the manufacture of the products can be found, for example

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'in the reports Schimmel & Co. 1929, pages 299 - 308, Rev. faculte is. univ. Istanbul 9 A, pages 105-114 (1944) refer to Chemical Abstracts (1946) column 3722. A process which not only involves the preparation of the unsaturated carboxylic acids to be used according to the invention on a laboratory scale, but also in a technically useful manner, is permitted in the German Offenlegungsschrift 2 121 635 described.

According to this method, v / ground in the 'chain length corresponding P hydroxynitriles, at temperatures of preferably 80 to 150 ⁰ C with an aqueous mineral acid treatment, the resulting products after separation of the aqueous phase at 100-400 C thermolyzed and the resulting carboxylic acids in a conventional manner. isolated. The ^ -hydroxycarboxonitriles to be used as starting materials in this preparation of the unsaturated carboxylic acids can be obtained particularly advantageously by reacting epoxides with hydrocyanic acid in the liquid phase and in the presence of strong bases and / or compounds which form cyanide ions as catalysts.

The unsaturated carboxylic acids produced economically by the last-mentioned process are water-configured and contain 80-96 % of ", ^ - unsaturated and 4-20% of ^, ^ - unsaturated carboxylic acids. In addition to the advantage of technically and economically good production possibilities, such products also have a very good antimicrobial effectiveness in the pH range ^ 5, which makes them particularly suitable for the use according to the invention. Those unsaturated carboxylic acids have proven to be particularly favorable, in which according to the aforementioned structural formula R. a

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Alkyl radical with 6-10 carbon atoms and η the number 0 represent, that is, «, / ^ - unsaturated carboxylic acids with a total carbon number of 9-15 such as 2-nonenecarboxylic acid, 2-decenecarboxylic acid, 2-undecenecarboxylic acid, 2-dodecenecarboxylic acid and 2-tridecenecarboxylic acid and of these, in turn, trans-2-nonenecarboxylic acid and trans-2-undecenoic acid are the best effective compounds.

Unsaturated carboxylic acids to be used according to the invention are, for example, 2-nonene, 2-decene, 2-undecene, 2-dodecene, 2-tridecene, 2-tetradecene, 2-pentadecene, 2-heptadecene, 2- Nonadecenoic acid, 3-nonene, 5-dscen, ^ -undecene - ^ - dodecenic, 5-tridecenoic acid, especially in the trans configuration, as well as mixtures of such οί, β- and β, γ -unsaturated carboxylic acids, especially mixtures of 8o - 96 % of #, / # - unsaturated carboxylic acids and 4 - 20 % of ß, γ- unsaturated carboxylic acids.

In the further development of the subject matter of the parent application, it was found that particularly advantageous Results in terms of antimicrobial effectiveness are obtained using the unsaturated carboxylic acids used in combination with formaldehyde.

The invention thus relates to the use of

unsaturated carboxylic acids according to patent

(Patent application P 23 10 246.7>, in which the unsaturated Carboxylic acids used in combination with formaldehyde will.

It was found that the unsaturated carboxylic acids in certain areas of application of the disinfection

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technology, e.g. surface disinfection, could not yet be fully satisfied, as it was necessary to achieve the desired Effects too high application concentrations were required. Formaldehyde, its antimicrobial efficacy is generally known, had to be used in concentrations alone to achieve satisfactory results are used that were no longer justifiable for reasons of odor nuisance.

Surprisingly, it has now been found that by combining the unsaturated carboxylic acids with formaldehyde a synergistic increase in effectiveness occurs in a manner that is satisfactory Allow the disinfection problems in question to be dealt with. The combination according to the invention is it is possible, with a good disinfecting effect, to reduce the active substance concentration as a whole as well as to unsaturated carboxylic acids and to lower formaldehyde to such an extent that the antimicrobial agents can be used without problems can.

The inventive combination of unsaturated carboxylic acids with formaldehyde can be converted into a wide variety of acidic Cleaning agents in the industrial sector, e.g. in acidic cleaning agents for dairies, breweries, food processing plants, in acidic surface disinfectants, in Disinfectants in the veterinary sector, e.g. in stable disinfectants. A special The combination of unsaturated carboxylic acids with formaldehyde is important in the area of surface disinfection in hospitals and similar institutions too.

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When used in antimicrobial detergents, the unsaturated carboxylic acids are used in an amount of 0.005-20, preferably 0.01-10 percent by weight and formaldehyde in an amount of 0.025-25, preferably 0.05-10 percent by weight, based on the total Detergent, used.

The following examples are intended to explain the subject matter of the invention in more detail without, however, referring to it restrict.

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The antimicrobial effectiveness of unsaturated carboxylic acids, of formaldehyde as well as the combination of unsaturated carboxylic acids with formaldehyde was made using determined by the suspension test. The methodology of this testing procedure is the guidelines for testing chemical disinfectant, published by the German Society for Hygiene and Microbiology (1959) taken. According to these guidelines, 0.1 ml of germ suspensions of the bacteria listed below were made pipetted into test tubes at a temperature of 18-21 ° C.

1. Staphylococcus aureus 5 x 10 'germs / ml

1 2 * Escherichia coli 4 χ 10 'germs / ml

To this end, 10 ml of the various dilution quantities of the substances to be tested were added to acidic aqueous solutions of various pH values. The concentrations of the unsaturated carboxylic acids to be used according to the invention were respectively 25, 50, 100 ppm, of formaldehyde 1 and 2 #. After exposure times of 1, 2 1/2, 5, 10, 20, 30, 40 and 60 minutes, the test tubes were each a loop material was removed and inoculated into 10 ml nutrient broth containing 0.1 % histidine to eliminate the bacteriostatic after-effects. The inoculated nutrient solutions were incubated at 57.degree. After 6 days, the cultures were assessed macroscopically for growth and in this way the killing times were determined, which are compiled in Table 1 below. The tests were carried out with the following substances:

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A) trans 2-nonenoic acid V95 % oL, ß- and i> 5% / 3, γ -unsaturated

B) trans 2-decenoic acid e ~ 85 # &, ß- and -U 5 $ ^, γ-unsaturated

C) trans 2-undecenoic acid a-90 # &, / & - and tdO $ ^, / - unsaturated

D) trans 2-dodecenoic acid ^ 92 f> e <> / 3- and -v8 ^^, ^ - unsaturated Ξ) trans 2-tridecenoic acid ^ 90 % &, / $ - and xlO $ / 3,} '- unsaturated

F) trans 2-pentadgenic acid ^ 85 $ £ *, / # - and "VL 5 ^ ^, - ^ - unsaturated

G) tx ^ anr; 2-heptadecenoic acid <v90 fo tk, ß- and 1.10 % β, γ -unsaturated H) trans 2-nonadecenoic acid · ν & 5 ^c po <, ß- and "V15 / &fö> y -unsaturated 1) 5-nonenic acid

K) formaldehyde -

Table 1

Killing times in different pH ranges in minutes Substance concentration germ 1 germ 2

pH 3 pH 4 pH 5 PH

K K 50 1 O ^
J. ok ι o ^
J. / 3 60 60 60 60 K K 100 2 % - 1 % 4o 40 40 40 A. K 50 ppm 'C. / Ό 5 20th 10 40 A. K 25th ppm O O ^
~ d. /O 2.5 10 5 20th A. + 50 ppm H 2.5 .10 5 10 A. + 25th ppm H 5 10 10 20th A. + K 50 ppm H - 1 % 1 5 2.5 10 A. + K 100 ppm λ ■ 2 fo 2.5 10 5 10 B. 25th ppm 10 20th 20th 120 B. 25th ppm 2.5 10 10 60 B. + ppm λ 10 20th 10 20th B. ppm λ 5 10 5 20th

C 50 ppm 5 20 10 20

C 100 ppm 2.5 5 5 10

C + K 50 ppm + 1 % 1 5 1 5

C + K 25 ppm + 1 fo 5 10 10 20

C + K 50 ppm + 2 f., 1 5 1 5

C + K 25 ppm + 2 fo 2.5 10 5 10

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Killing times in different pH ranges in minutes substance concentration germ 1 germ 2

pH 5 pH 4 pH 3 pH 4

D. K 50 ppm 10 20th 10 6o D. K 100 ppm 2.5 10 10 50 .D + 25th ppm H 5 20th 10 20th D. ⁺ 25th ppm H 5 10 5 20th E. K 50 ppm 10 20th 20th 120 E. K 100 ppm 2.5 10 10 60 E. + 25th ppm H 5 20th 10 · 50 E. ⁺ 25th ppm 4 5 10 5 20th F. K 50 ppm 10 50 50 120 F. K 100 ppm 5 20th 20th 60 F. + 25th ppm 4 5 • 20th 20th 60 F. ⁺ 25th ppm 4 5 10 10 50 G K 50 ppm 50 6o 60 120 G K 100 ppm 20th 50 40 120 G + 50 ppm 4 10 20th 10 40. G ⁺ 50 ppm 4 5 20th 10 50 H K 50 ppm 6o 120 120 120 H K 100 ppm 50 120 60 "120 H + 50 ppm 4 20th 40 50 40 H ⁺ 50 ppm 4 10 50 20th 40 J K 50 ppm 50 6o 60 120 J K 100 ppm 10 50 20th 60 J + 50 ppm 4 10 20th 20th 40 J ⁺ 50 ppm 4 5 20th 10 20th l · I / o - 1% - ■ & - 1% ■ 2% ■ ι% ■ 2% ■ i%

The pH fourth was adjusted with hydrochloric acid citrate buffer

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In the following experiment, the germicidal effect of the individual components and the combination in surface disinfection on Staphylococcus aureus was investigated. Lacquered wooden boards (6x6 cm) and PVC flooring (6x6 cm) were used as test areas. To contaminate the surfaces, mixtures of germ suspensions were used, which were prepared by washing away 16-hour cultures J5 of different strains of Staphylococcus aureus from glass dishes with 5 ml of broth. 3 drops of the germ suspension (germ density 1 ~ 3 × 10 germs / ml) were pipetted onto each test area and evenly distributed with a glass spatula. After the surfaces had dried, they were disinfected by thorough wetting with the active ingredient solutions given in Table 2. After 1, 2, 4 and 6 hours of exposure, a quarter of each of the treated areas was thoroughly rubbed with a moistened cotton swab to remove the germs. The swab was spread on broth agar containing 0.1% histidine to eliminate the bacteriostatic aftereffect. "The evaluation was carried out after 72 hours of incubation at 27 ° C. The killing times or the respective reduction in the number of germs on the surface after a certain time can be found in Table 2 below.

In the table, the characters have the following meanings:

+++ = 250 germs per plate and above ++ = 50 - 250 germs
+ = 10 - 50 germs
Numbers = number of germs

=; no germs could be detected.

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Table 2

Germicidal effect on the surface (wood, PVC)

Test germ: Staphylococcus aureus. Initial bacterial count 13 χ 10 / ml

Substance Concentration pH value wood (hours) PVC (hours) in% 12461246

'K 0.05
0.025 3 ■ +++ +++ ++ ++ -ι 0.05
0.025 4th _{+++ +++ +++ +++} , B 0.05,
0.025 3 ++ ++ + + + 0.05
0.025 4th +++ ++ + + + B + K 0.05 + 0.05
0.025 + 0.05
0.05 + 0.025
0.025 + 0.025 3 +++ 35 +
++ 10 3 - +
++ + + 10 + 0.05 + 0.05
0.025 + 0.05 4th ++ + 10 1 +
++ + + 5 + - +++++ +
- ++ +++ ++ + ■ ++ ++ + +
- ++ +++ ++ + ++ ++ + 10
++ ++ + + ++ ++ + +
++ +++ ++ ++ 10 -
+ +35
5-1
+ + 10 5 + +54
+ + + 7

0.05 + 0.025 0.025 + 0.025

10 3

0.05 3.025

0.05 0.025

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Germicidal effect on the surface (wood, PVC)

9 Test germ: Staphylococcus aureus, initial germ count 13 χ 10 / ml

Substance concentration pH value wood (hours) PVC (hours) in% 12 4 6 12 4 6

C + K 0.05 + 0.05 0.025 + 0.05 0.05 + 0.025 0.025 + 0.025

0.05 + 0.05 0.025 + 0.05 0.05 + 0.025 0.025 + 0.025 5

2

+ 3 + 3

10

5

+

2

+ 5

10 3 10 10 5

0.05
0.025

0.05
0.025

G + K 0.05 + 0.05 0.025 + 0.05 0.05 + 0.025 0.025 + 0.025

0.05 +0.05 0.025 + 0.05 0.05 + 0.025 0.025 + 0.025

++ + 10 7

9 3 + 8 5 -5

8 2

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Below are compositions for acidic antimicrobial Means indicated. The remedies generally come in 0.25-2%, preferably 0.5-1.5% Concentration at work.

Antimicrobial acidic detergent for the beverage industry

Phosphoric acid (8o # ig) 50 Parts by weight 35 Parts by weight Surface disinfectants for hospitals 4th Oewioht parts Nonylphenol + 9 ethylene oxide 4th dd 35 dd Nonylphenol + 9 ethylene oxide 5 M. Nitrilotriacetic acid 4th dd 4th dd Phosphoric acid 80 # ig 20th 1" Substance C 2.5 dd 1 dd 35 # formaldehyde solution 2.5 It 35% formaldehyde solution 15th dd 2.5 Il. Substance C 68.5 It water ■ 24.5 It 17.5 Il water Antimicrobial acidic detergent for industry 5 It Phosphoric acid 80% Sulfuric acid 75% Nonylphenol +. 9 ethylene oxide Corrosion inhibitor Substance A 35 # formaldehyde solution water

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Claims (2)

HENKEL & CIE GMBH s / k 13 rur ^ tanm.idunffT 4772 23A9090 patent claims 1. Use of unsaturated carboxylic acids according to Patent (patent application P 23 10 246.7), characterized in that the unsaturated carboxylic acids are used in combination with formaldehyde v / earth. 2. Use of unsaturated carboxylic acids according to claim 1, characterized in that the unsaturated Carboxylic acids in an amount of 0.005-20, preferably 0.01-10 percent by weight and formaldehyde in an amount of 0.025-25, preferably 0.05 percent by weight, based on those containing them antimicrobial agents are used. MSI1S / 107S 509815/1075