DE1280457B - Antibacterial soaps, detergents and skin treatment agents - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

German KL:

Number:
File number:
Registration date:
Display day:

ClId

A 611
C 07 c

23e-4

3Oi-3; 12 ο-17/03;
12 q-29/01

P 12 80 457.8-41 (P 31927)

May 31, 1963

17th October 1968

The invention relates to antibacterial soaps, detergents and skin treatment agents that are characterized in that they are a ternary mixture as an antibacterial component contains from

1. at least one halogenated salicylanilide der general structural formula

in which Z is hydrogen, halogen or trifluoromethyl means Xi is halogen or ethoxy, Xo is hydrogen or halogen and Y Means hydrogen or trifluoromethyl, and at least one polyhalosubstituted Carbanilide of the general structural formula

NH-C-NH

Il ο

in which X is a halogen, Y is hydrogen or a halogen, at least one of which of the Y atoms is a halogen atom and wherein the ratio of (1) to (2) is between about 20: 1 and 1:20, the ratio of (2) to (3) between about 20: 1 and 1:20 and the ratio of (1) to (3) is between about 20: 1 and 1:20.

Preferred salicylanilide compounds are 3,5,4'-tribromosalicylanilide, 5-bromosalicyl-3,5-di (trifluoromethyl) anilide. 5-chlorosalicyl-3,5-di (trifluoromethyl) anilide. 3.5 - dichlorosalicylic - 3,4 - dichloroanilide and

Soaps with antibacterial effects, detergents
and skin treatment agents

in which Xi is hydrogen or halogen, Xz is a halogen and Y is hydrogen, halogen or triiuormethyl, 2. at least one trifluoromethyldiphenylurea compound of the general structural formula

Il

NHCNH

Applicant:

The Procter & Gamble Company,
Cincinnati, Ohio (V. St. A.)

Representative:

Dr. W. Beil, A. Hoeppener and Dr. H. J. Wolff,

Lawyers,

6230 Frankfurt-Höchst, Adelonstr. 58

Named as inventor:
Wilfred Samuel Martin,
Cincinnati, Ohio (V. St. A.)

Claimed priority:

Belgium of June 7, 1962 (493 968)

S-ChlorsalicyM-trifluoromethyl ^ -chloranilide. Other halogenated salicylanilides, which correspond to the above general formula and in connection with Other compounds described show synergistic activity are disclosed in the U.S. Patent 2 703 332.

The preferred trifluoromethyldiphenylurea compounds include 3-trifluoromethyl-4,4'-dichlorocarbanilide, S-trifluoromethyW ^^ '- trichlorocarbanilide, 3,3'-bis- (trifluoromethyl) -4-ethoxy-4'-chlorocarbanilide and 3,5-bis- (trifluoromethyl) -4-chlorocarbanilide. These and other halogenated trifluoromethyldiphenylurea compounds that can be used are described in detail in U.S. Patent 2,745,874.

Preferred halogen-substituted carbanilide compounds are 3,3 ', 4'-trichlorocarbanilide and 3,4,4'-trichlorocarbanilide. Other suitable compounds are z. B. 3,3 ', 4-tribromocarbanilide, 3,3', 4 ', 5'-tetrachlorocarbanilide, 3,3 ', 4'-tribromocarbanilide and others described in U.S. Patent 2,846,398 are.

There have been many different compounds for use as antibacterial agents in Soaps, detergents, cleansing creams and similar products, such as B. Antiperspirant

809 6271408

agents and deodorants, suggested. Among the earliest compounds approved for use in the Soaps suggested include the phenols and the phenolic fatty acid esters. Later found certain Mercury compounds use. Recently, means like. certain halogenated Bisphenols, of which hexachlorophene or C-II is the best known, the halogenated salicylanilides and the halogenated carbanilides, used in soaps, detergents and other products.

For example, the German Auslegeschrift 1009 750 describes soap-containing detergents and cleaning agents, which contain halogenated carbanilides, which German Auslegeschrift 1017 312 describes Soaps that contain a halogenated bisphenol in addition to 3,4,4'-trichlorocarbanilide, and the Swiss Patent 300 565 describes the use of a halogenated salicylanilide in detergents.

However, the person skilled in the art knows that many of the above-mentioned compounds can only be used with restrictions can be used. For example, they have been found to be effective in aqueous solution Phenols and phenol esters in soaps or detergents are ineffective. Other of the antibacterial agents mentioned are only against a small group of organisms, especially gram-positive ones. The halogenated bisphenols are well known sensitive to light and discolour with prolonged exposure to sunlight. When incorporated into soap or Detergent bars in sufficient quantities to achieve good antibacterial effectiveness, d. H. up to 2% or more, the soap is discolored by the bisphenolic compounds strong that the bar must be colored yellow to hide the discoloration.

Some of the compounds proposed so far, while being relatively good antibacterial agents are not usable because they are present in the products in relatively large quantities must be, d. H. up to 2 to 3 percent by weight, based on the total weight of the cleaning product, making the product too expensive.

Some of these problems could be resolved by the discovery that certain binary mixtures of antibacterial agents show synergistic effects. Synergistic mixtures of antibacterial Means such as B. halogenated bisphenols and halogenated carbanilides, halogenated bisphenols and halogenated salicylanilides have already been described. Real synergistic mixtures however, antibacterial agents are relatively rare, and the synergistic effectiveness such mixtures are unpredictable at all. But there is an urgent need for effective ones antibacterial agents with increased substantivity to the skin.

It has now been found that a mixture of a halogenated trifluoromethyldiphenylurea compound, a halogenated carbanilide and a halogenated salicylanilide produce a surprising synergistic effect Shows effectiveness. Are these compounds in soaps or detergents or the like Products for personal use incorporated, then they form a synergistic mixture, which is effective in low concentrations.

The following combinations of various antibacterial agents according to the invention have synergistic properties Effect on:

3,4,4'-trichlorocarbanilide;
3-trifluoromethyl-4,4'-dichlorocarbanilide;
3,5,4'-tribromosalicylanilide;
S-TriffuormethyW ^^ '- trichlorocarbanilide;
3,4,4'-tribromocarbanilide;
S-BromsalicyW ^ '- di-itrirluormethy ^ -anilid;

3,4,3 ', 4'-tetrachlorocarbanilide;
S-TrifluoromethyM ^ '- dichlorocarbanilide;
S ^ '- dichlorosalicylanilide;

3,4,3 '^' - tetrachlorocarbanilide;
3,5,4'-tribromosalicylanilide;
3,5-bis (trifluoromethyl) -4-chlorocarbanilide;

3-trifluoromethyl-4,4'-dichlorocarbanilide;
3,3 ', 4-trichlorocarbanilide;
3,5,4'-tribromosalicylanilide;

3,5,4'-tribromosalicylanilide;
3,4,3 ', 4'-tetrachlorocarbanilide;
3,3'-bis (trifluoromethyl) -4-ethoxy-4'-chlorocarbanilide;

S ^ '- dichlorosalicylanilide;
3'-bromo-3,4-dichlorocarbanilide;
3-trifluoromethyl-4,4'-dichlorocarbanilide;

3,5,4'-tribromomicylanilide;
3-trifluoromethyl-4,4'-dichlorocarbanilide;
3,4,4'-tribromocarbanilide;

3,5,4'-tribromosalicylamide;
3,4,3'-trichlorocarbanilide;
3-trifluoromethyl-4,4'-dichlorocarbanilide.

The blends listed above show a synergistic antibacterial effect when used in Soaps and detergents and other products, such as B. antiperspirant agents and Deodorants.

example 1

In this example, the antibacterial synergism of the preparations according to the invention is shown in a skin retention test. In this experiment, callous skin was removed from the sole of the foot and cut into small (about 2 to 3 mm large) cubes. These were washed in a normal concentration soap product containing the antibacterial compound (s). The test usually lasted 5 minutes; the temperature was 48 ° C. (The soap was a mixture of 80% sodium tallow soap and 20% sodium coconut oil soap.) After washing, the cubes were rinsed thoroughly with distilled water to remove all traces of soap and then allowed to dry. The dry skin cubes were embedded in molten agar which had previously been inoculated with the test organism, in this case with gram-positive coccus and gram-positive rod bacteria, two common types of bacteria that appear on the surface of the skin; then the agar plates with the skin cubes were placed in a refrigerator overnight to allow the antimicrobial agent to spread from the skin into the surrounding medium. The next day, the plates were placed in an incubator with a temperature of 37 ^° C., and the organisms were allowed to grow for 24 to 48 hours. The clear zone of growth inhibition of the test organisms surrounding the cubes is an indication that the skin cubes were given antimicrobial activity during the washing process.

Skin retention experiment

Diameter of sterile zones (mm),

which the washed with the product

Skin cubes surrounded

product

1. Soap

2. Soap + 0.333%
3,5,4'-tribromosalicylanilide + 0.333%
3-trifluoromethyl-4,4'-dichlorocarbanilide + 0.333%
3,4,3'-trichlorocarbanilide

Type of organism that
isolated from human skin

Grief + coccus

15th

Gram + rod bacteria

13th

From the table above it can be seen that the synergistic blends of the present invention excellent antibacterial properties over the common ones found on the skin Show organisms.

B e i s ρ i e 1 2

In this example the synergism becomes that of the invention Compounds shown by means of a deodorant test. The attempt is made on the carried out in the following way:

At the beginning of a week, a group of 126 men were given bars of ordinary toilet soap passed, e.g. B. Toilet soap made from pilierter soap and a synthetic detergent (which is a Mixture of 20% potassium alkyl sulfate, 8% sodium alkyl glyceryl ether sulfonai, 33.8% of a mixture of 20:80 coconut to tallow sodium soap and 17.0% of a mixture of 20:80 coconut Sebum-fatty acid-potassium soap), with the instruction to use this bar for bathing for 4 days use. On the evening of the 4th day, each test person is observed how they look after a Standard scheme washes. After that, the test subjects are instructed not to turn up before the late The afternoon of the following day to wash under her arms. At this point the armpits become each test subject was smelled independently by four experts and the intensity of the Odor under each arm classified according to a standard scale (with 0 no body odor and 10 one means very strong and unpleasant body odor, while the remaining numbers are between 1 and 10 Represent intermediate values). Now each test person receives a test bar, which lists the ones to be examined contains antibacterial agents and a second bar that does not contain any additive. The first Tie is used under one arm and the second tie is used under the other arm. These arrangements are adapted to normal smell. The test subjects wash twice a day for 6 days their arms (mornings and afternoons) under supervision, with a standard washing process under them The assigned bars are used.

The next morning there is no washing. In the late afternoon of the 7th day, about 24 hours after the last wash, the odor strength under each arm is again determined by four experts according to the above Description classified. The twice daily monitored washings then become another Week continued, and after the end of the second week, the odor strength will again be according to the description classified. The mean value and the relative deodorizing effectiveness are calculated from the ratings the trial bar is determined. The above procedure is repeated for each latch repeated containing the antibacterial agent to be tested.

Deodorizing effect

product

1. Soap alone (toilet bar made from pilietter soap and synthetic detergent

middle)

2. Soap + 0.333% 3,4,3'-trichlorocarbanilide

+ 0.333% 3,5,4'-tribromosalicylanilide

+ 0.333% 3-trifluoromethyl-4,4'-dichlorocarbanilide

3. Soap + 0.333% 3-trifluoromethyl-4,4'-dichlorocarbanilide

+ 0.333% 3,4,4'-trichlorocarbanilide

+ 0.333% of a mixture of 60:40 3,5,4'-tribromosalicylanilide and 4,5'-dibromosalicylanilide

3 A ^ -Trichlorocarbanilide

a 60:40 mixture of 3,5,4'-tribromosalicylanilide and 4,5-di-

bromosalicylanilide
3-trifluoromethyl-4,4'-dichlorocarbanilide

4. Soap + 0.15%.
+ 0.700 / o

+ 0.15%

From the above figures, it can be seen that the synergistic antibacterial preparations of the present Invention have a significant deodorizing effectiveness when added to a soap or detergent, agents can be added.

Average
odor

5.11

4.16

4.27

4.32

EXAMPLE 3

This example shows the synergism of the mixture of antibacterial agents described herein in a soap by means of a hand washing experiment

shows. This experiment is a modification of the well-known Cade handwashing experiment (Arthur R. C a d e, Papers on Evaluation of Soaps and Detergents, 'Special Technical Publication No. 115, published by the American Society of Testing Materials, 1952) and can be described as follows.

A group of 10 test persons is given a test bar containing the antibacterial agent or mixtures of agents and intended for home use, and also a bar for use at work. Hands are washed at least three times on day ^{1 for 4 days.} On the 5th day the hands are washed five times in a row, the last time with a measured amount of sterile distilled water. Hands are carefully rinsed in basin water and a sample of the wash water is immediately taken for bacterial counts. The sample is filtered and the bacteria collected on the filter are transferred to a nutrient medium in sterile Petri plates and incubated for 48 hours at 37 ° C. The number of colonies that appear is counted. The number of organisms contained in the fifth tank can be calculated from the size of the amount used.

The number of organisms removed during the wash is proportional to the total number on the Skin. By comparing the number of organisms removed on the 5th day after using the experimental bar with that removed after using the untreated bar under the same conditions Number one can estimate the germicidal effectiveness of the bar. It is common to see the results express as "% reduction in removable bacteria" versus control.

Hand washing attempts

Percentage reduction in the average number of organisms found during the fifth attempt a series of standardized handwashes after one week of exclusive use of the Product have been removed.

product

⁰ I.

reduction

Soap alone
soap

+ 1%

+ 0.66%
+ 0.66%
+ 0.66%

+ 0.333%
+ 0.333%
+ 0.333%

3,5,4'-tribromosalicylanilide S-trifluoromethyM ^ '- dichlorocarbanilide 3,4,4'-trichlorocarbanilide

3,5,4'-tribromosalicylanilide 3-trifluoromethyl-4,4'-dichlorocarbanilide 3,4,4'-trichlorocarbanilide

3,5,4'-tribromosalicyanilide 3-trifluoromethyl-4,4'-dichlorocarbanilide 3,4,4'-trichlorocarbanilide

Soap + 0.666% a 60:40 mixture of 3,5,4'-tribromosalicylanilide and 4,5'-dibromo-

salicylanilide

3-trifluoromethyl-4,4'-dichlorocarbanilide 3,4,4'-trichlorocarbanilide

+ 0.666%
+ 0.666%

+ 0.28%
+ 0.28%
+ 0.44%

3,5,4'-tribromosalicylanilide 3-trifluoromethyl-4,4'-dichlorocarbanilide 3,4,4'-trichlorocarbanilide

no

99.4

99.1

97.0

99.7

98.4

When examining the above table one can compare to known bacterial mixtures or 50 determine that the synergistic preparations of the before- to the mixture components alone have, invention in soap have significant antibacterial activity.

In order to show the superior effect that the ternary antibacterial mixtures according to the invention in the the hand washing tests described above were repeated with the following products, whereby the stated results were obtained.

product

reduction

Soap + 0.166% 3,5,4'-tribromosalicylanilide

+ 0.166% S-trifluoromethyM ^ '- dichlorocarbanilide

+ 0.166% 3,4,4'-trichlorocarbanilide

Soap + 0.50% 3,4,4'-trichlorocarbanilide

Soap + 0.50% 3-trifluoromethyl-4,4'-dichlorocarbanilide

83 *)

66

67

Mixture according to the invention.

continuation

10

product

reduction

Soap + 0.50% 3,5,4'-tribromosalicylanilide

Soap + 0.50% 2,2'-dihydroxy-3,5,6,3 ', 5', 6'-hexachlorodiphenyl methane

Soap + 0.333% 3,5,4'-tribromosalicylanilide

+ 0.333% 3-trifluoromethyl-4,4'-dichlorocarbanilide

+ 0.333%. 3,4,4'-trichlorocarbanilide

+ 0.50% 3,4,4'-trichlorocarbanilide

+ 0.50% 2,2'-dihydroxy-3,5,6,3 ', 5 ^/ , 6'-hexachlorodiphenyl methane

*) Mixture according to the invention.

70 70

97 *)
82.9

To prove the superiority of the ternary mixture used according to the invention over that from the Argentine patent specification 106,388 known binary mixtures, comparative tests were carried out. The bacteriostatic "breakthrough point" of soaps, which is an inventive ternary mixture contain, determined and the "break-through point" of soaps, the binary Mixture of the Argentine patent contain. The "breakthrough point" is the minimum concentration which prevents the growth of Staphylococcus aureus FDA 209 ATCC 6538.

The experimental arrangement comes from P e 1 c a r and Reid "Microbiology" (1958), pp. 235, 253 bis 255. These are common attempts to evaluate the effectiveness of antiseptic agents.

product Breakthrough Point (Parts per Million parts 3,5,4'-tribromosalicylic total anilide product) Soap - 3,4,4'-trichlorocarb- anilide 3-trifluoromethyl 4,4'-dichlorocarbon anilide 3,5,4'-TrIDrOmSaIiCyI- 10 anilide Soap - 3,4,4'-trichlorocarbon anilide 3,5,4'-TrIbTOmSaIiCyI- 15th aniliQ
3,4,4'-trichlorocarbon Soap - anilide 3-trifluoromethyl 4,4'-dichlorocarbon anilide 3,5,4'-tribromosalicylic 5.5 anilide Soap - 3,4,4'-trichlorocarbon anilide 7.5 (- 0.166% h 0.1660 / " l 0.166% 0.5o / o r- 0.250 / o r- 0.250 / o 0.50 / ₀ I-0.3330 / o f- 0.333% l 0.3330 / 0 1.00 / 0 I- 0.5% ι- 0.50 / 0

1.0%

Relatively small amounts of the synergistic antibacterial compositions of the present invention Invention are enough to make a soap antibacterial. The term "soap" is used here in general Meaning used as the term doesn't just refer to the ordinary sodium or potassium soap refers, which by the saponification of fat or fatty acids as natural anionic detergents but also to products made from synthetic anionic and nonionic detergents in liquid, pasty, solid, flaky, granular or other similar form. One calls a soap as "antibacterial" if it is effective against the Staphylococcus aureus organism, independently whether it is also effective against any type of bacteria.

Due to the synergistic effectiveness of the compounds according to the invention, the soap smaller amounts than usual with the usual antibacterial agents, incorporated and still good antibacterial effectiveness can be achieved. Quantities of only V2 to 1% of the synergistic ones described here Mixtures based on the weight of the total soap bar or cleaning product have been proven is found to be satisfactory, but it is preferred to use 1 to 2% of the mixtures, based on the total weight of the bar or cleaning product. The upper limit of the under for practical and economic considerations, the amount of the agent is usually about 5%. The proportions of the individual antibacterial compounds of the present invention can vary between about 20: 1 and 1:20, the preferred proportion is about 1: 1: 1.

In general, increasing the concentration of the synergistic mixture increases the germicidal one Effectiveness of soap products. It turns out, however, that the cost of the agent in the soap or prevent the shampoo from being used in excess. Will the soap be a too large amount of the agent incorporated, so the cleaning properties of the soap or the detergent decrease.

The anionic synthetic detergent usable in the present invention is general a water-soluble salt of an organic sulfuric acid compound having an alkyl group about 8 to about 22 carbon atoms and a residue such as e.g. B. a sulfonic acid or sulfuric acid ester residue, contains. Important examples of the synthetic compounds that belong to this group can be improved by incorporating the mixtures according to the invention, the sodium or

809 627 / 140S

Potassium alkyl sulfates, especially those produced by sulfating higher alcohols formed by reducing glycerides of tallow or coconut oil, sodium or potassium alkyl benzene sulfonates, especially those described in U.S. Patents 2,220,099 and 2,477,383 wherein the alkyl group contains from about 9 to about 15 carbon atoms; Sodium alkyl glyceryl ether sulfonates, especially those ethers in which the alkyl group is derived from the higher alcohols of tallow and coconut oil; Sodium coconut oil fatty acid monoglyceride sulfates and sulfonates, sodium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 3 moles of ethylene oxide and other compounds known to the person skilled in the art, a number of which are in the USA patents 2,486,921 and 2,486,922 are described.

Other anionic sulfonate surfactants useful in the present invention are sulfonated alkyl acid amides, such as. B.

Ci ₇ H ₃₃ CON (CH ₃ ) CH ₂ SO ₃ Na the sulfonated esters, such as. B.

RCOOCH ₂ CH ₂ SO ₃ Na

wherein R is an alkyl radical having 11 to 17 carbon atoms, the sodium salt of the bisulfate of a dialkyl dicarboxylate, the sodium salt of sulfenic acid derivatives of a dialkyl dicarboxylate, sodium sulfosuccin ester, such as B.

NaCOCCH ₂ CH (SO ₃ Na) CONHCi ₈ H ₃₇ and the like.

The above nonionic synthetic detergents, which are characterized by the synergistic Antibacterial compositions of the present invention can be improved generally as compounds denote that by condensation of alkylene oxide groups with an organic hydrophobic Compound of aliphatic or alkyl aromatic nature can be prepared, e.g. B. Condensation Products of alkylphenols having a straight or branched chain alkyl group of about 6 to 12 carbon atoms, with about 10 to about 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in each compound can expediently of polymerized propylene diisobutylene, Octane or nonane or any other natural or artificial source that contains alkyl chains with the required number of carbon atoms.

For example, one known group of nonionic compounds is formed by incorporation smaller amounts of the synergistic blends of the present invention are antibacterial Effectiveness obtained by condensation of ethylene oxide with a hydrophobic one obtained by condensation of propylene oxide with propylene glycol Basic substance produced.

Other suitable nonionic compounds can be obtained by condensing ethylene oxide with the product of the reaction of propylene oxide and ethylene diamine.

A small amount totaling about 2% of a 2: 2: 1 mixture of 3,5,4'-tribromosalicylanilide, 3-trifluoromethyl-4,4'-dichlorocarbanilide and 3,4,4'-trichlorocarbanilide makes z. B. a preparation which one or the other of the above cleaning agents or mixture containing, against a wide range of microorganisms, some of which are gram-negative, have an antibacterial effect. It was found that the synergistic mixtures of the present invention the antibacterial effectiveness of soap and soap-free synthetic Detergents in bar and granular form and incorporated into the soap by any suitable method which could be an even distribution of antibacterial agents throughout Mass guaranteed.

Regular use of a soap bar that contains 1.5% of the synergistic properties of the invention Contains mixtures leads to a considerable reduction in the bacterial population of the skin and thereby noticeably reduces the body odor, which is due to the bacterial decomposition of body sweat is due.

This is followed by an example of the composition of a piled toilet soap ("middle fraction" refers to a fraction of distilled coconut alcohol, which is predominantly made from lauryl and myristyl alcohols):

20.0% potassium alkyl sulfate (alkyl group from the middle fraction of the catalytic reduction alcohols obtained from coconut oil);

8.0% sodium alkyl glyceryl ether sulfonate (alkyl group from the middle fraction of alcohols produced by the catalytic reduction of coconut oil); 33.81% sodium soap from 20:80 coconut too

Tallow fatty acids;
17.07% magnesium soap from 20:80 coconut

to tallow fatty acids;
5.81% inorganic salts;
0.33% 3,4,4'-trichlorocarbanilide; 0.33% 3,5,4'-tribromosalicylanilide; 0.33% S-trifluoromethyl - ^ '- dichlorocarbanilide; 8.0% moisture;
Rest: Various.

A granular, synthetic anionic cleaning agent with the addition of the inventive detergent antibacterial agent can be prepared according to the following recipe:

17.5% sodium alkylbenzenesulfonate (the alkyl radical has an average of about 12 carbon atoms and derived from polypropylene);

49.7% sodium tripolyphosphate; 13.3% sodium sulfate;
7.0% silicate solids;
0.75% 3,5,4'-tribromosalicylanilide; 0.75% 3,4,3'-trichlorocarbanilide; 0.75% 3-trifluoromethyl-4,4'-dichlorocarbanilide; ■ remainder: water and miscellaneous.

The antibacterial mixtures according to the invention can not only be used in toilet soaps and detergents, but also with the same success in others

Products such as shampoos, antiseptic ointments, foot powders, antiperspirants, deodorants and the like.

Claims (1)

Patent claims: 1. Antibacterial soaps, detergents and skin treatment agents, marked by a content of 1. at least one halogenated salicylanilide of the general structural formula X ₁ OH X ₁ Y in which Xi is hydrogen or halogen, X2 is a halogen and Y is hydrogen, halogen or trifluoromethyl, 2. at least one trifluoromethyldiphenylurea compound the general structural formula 30th 3. at least one polyhalosubstituted carbanilide of the general structural formula NH-C-NH Il ο in which X is a halogen, Y is hydrogen or a halogen, where at least one of the Y atoms is a halogen atom, and wherein the ratio of (1) to (2) is between about 20: 1 and 1:20, the ratio of (2) to (3) between about 20: 1 and 1:20 and the ratio of (1) to (3) is between about 20: 1 and 1:20. 2. Antibacterial soaps, detergents and skin treatment agents according to claim 1, characterized characterized in that the halogenated carbanilide is 3,4,4'-trichlorocarbanilide. 3. Antibacterial soaps, detergents and skin treatment agents according to claim 1, characterized in that the halogenated salicylanilide is 3,5,4'-tribromosalicylanilide. 4. Antibacterial soaps, detergents and skin treatment agents according to claim 1, characterized in that the trifluoromethyldiphenylurea compound 3 - is trifluoromethyl-4,4'-dichlorocarbanilide. in which Z is hydrogen, halogen or tri- Documents considered: fluoromethyl means, Xi halogen or German Auslegeschriften No. 1 017 312, Is ethoxy, X2 is hydrogen or halogen 35 1,097,750; and Y represents hydrogen or trifluoromethyl means, and Swiss Patent No. 300 565;
Argentine Patent No. 106 388. S09 627 / 140S 10.6t θ Bundesdruckelei Berlin