CA2582797C - Concentrated liquid formulations comprising a microbicidally active ingredient - Google Patents

Abstract

The application describes concentrated liquid formulations (b) comprising (b1) 5.1 to 30% by weight of microbicidally active ingredient, (b2) 0 to 80% by weight of sulfonate, (b3) 1 to 60% by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid; (b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof, and water to 100%, it always being necessary for one of the components (b2) or (b4) to be present. The formulations according to the invention are used as microbicidally active ingredient in cosmetic products, household articles or hand disinfectants, as preservatives in household articles and cosmetic products and as disinfectant and decontamination agent for textile fibre materials or the skin and hard surfaces.

Description

1 1 u 14 29276-740b CONCENTRATED LIQUID FORMULATIONS COMPRISING A MICROBICIDALLY ACTIVE INGREDIENT
This is a divisional application of Canadian Application S/N 2,252,555, filed on May 22, 1997.

The present invention relates to liquid formulations comprising microbicidally active ingredients and to the use of these formulations as microbicidally active ingredient in cosmetic products, household articles or hand disinfectants and to the use as preservatives in household articles and cosmetic products.

The parent application describes concentrated liquid formulations (a) comprising (a,) 1 to 80% by weight of a microbicidally active ingredient, (a2) 20 to 99% by weight of a mono- or dihydric alcohol or mixtures thereof, In one aspect, the present divisional application provides a concentrated liquid formulations (b) comprising (b1) 5.1 to 30% by weight of a microbicidally active ingredient, (b2) 0 to 80% by weight of a sulfonate, (b3) 1 to 60% by weight of a C1-C11monocarboxylic acid or of a C3 C12di- or -polycarboxylic acid;
(b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof, and water to 100%, it always being necessary for one of the components (b2) or (b4) to be present.

The liquid formulation (a) preferably comprises (a,) 20 to 70% by weight of a microbicidally active ingredient and (a2) 30 to 80% by weight of a mono- or dihydric alcohol or mixtures thereof.
Formulation (b) preferably comprises (b1) 10 to 30% by weight of a microbicidally active ingredient, (b2) 0 to 80% by weight of a sulfonate, (b3) 1 to 60% by weight of a C,-Ct1monocarboxylic acid or of a C3-C,2di- or -polycarboxylic acid;
(b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof, I 1 w 11=

and water to 100%.

Component (a,) or (b) is, in particular, 2-hydroxydiphenyl ether, of the formula Yo O Y

(1) l (OH) Z OH

(OH) M
in which Y is chlorine or bromine, Z is SOZH, NO2 or C,-C4alkyi, r is0to3, o is0to3, p is0orl, m is 0 or 1 and n is0orl.

Especially interesting compounds of the formula (1) are those in which Y is chlorine or bromine, m is 0, n is0orl, o is 1 or 2, r is 1 or 2 and p is 0.

Very especially interesting compounds of the formula (1) are those in which Y is chlorine, m is 0, n is 0, o is 1, r is 2 and p is 0.

I. 1 x .M

Very especially preferred is the compound of the formula (2) CI -Q- O P CI

OH CI

Other suitable microbicidally active ingredients which correspond to component (a1) or (b) are - phenol derivatives, - diphenyl compounds, - benzyl alcohols, - chlorhexidine, - C12 C14alkylbetaines and Ce Ct8fatty acid amido alkylbetaines, - amphoteric surfactants, - trihalocarbanilides and - quaternary ammonium salts.

The phenol derivatives are preferably compounds of the formula OH

(3) in which R1 is hydrogen, hydroxyl, C1-C4alkyl, chlorine, nitro, phenyl or benzyl, R2 is hydrogen, hydroxyl, C1-C6alkyl or halogen, R3 is hydrogen, C1-C6alkyl, hydroxyl, chlorine, nitro or a sulfur in the form of its alkali metal salts or ammonium salts, R4 is hydrogen or methyl and R5 is hydrogen or nitro.

1 1.-M

Halogen is bromine or, preferably, chlorine.

Examples of such compounds are chlorophenols (o-, m-, p-), 2,4-dichlorophenol, p-nitrophenol, picric acid, xylenol, p-chloro-m-xylenol, cresols (o-, m-, p-), p-chloro-m-cresol, pyrocatechol, resorcinol, 4-n-hexylresorcinol, pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol, o-phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol and 4-phenolsulfonic acid.

The Biphenyl compounds are preferably compounds of the formula R 'I R'2 Ri R2 (4) R13 X R3 in which X is sulfur or the methylene group, R, and R', are hydroxyl and R2, R'2, R3, R'3, R4, R'4, R5 and R'5, independently of one another, are hydrogen or halogen.

Examples of compounds of the formula (4) are hexachlorophene, tetrachloro-phene, dichlorophene, 2,3-dihydroxy-5,5'-dichlorodiphenyi sulfide, 2,2'-dihydroxy-3,3',5,5'-tetrachlorodiphenyl sulfide, 2,2'-dihydroxy-3,3',5,5',6,6'-hexachloro-diphenyl sulfide and 3,3'-dibromo-5,5'-dichloro-2,2'-dihydroxydiphenylamine.

The benzyl alcohols are preferably those of the formula R5 , RI

(5) \ 1 in which R1, R2, R3, R4 and R5, independently of one another, are hydrogen or chlorine.

I .I I.1.I/

Examples of compounds of the formula (5) are benzyl alcohol, 2,4-, 3,5- or 2,6-dichlorobenzyl alcohol and trichlorobenzyl alcohol.

Chlorhexidine can be employed as such or in the form of its salt with organic and inorganic acids.

An example which may be mentioned of C$ C18fatty acid amidoalkylbetaine is coconut fatty acid C8 C18amidopropylbetaine.

Examples of suitable amphoteric surfactants are C12alkylamino-, C1-C3alkanecarboxylic acids, for example alkylaminoacetic acids or alkylaminopropionic acids.

Trihalocarbanilides are, in particular, those of the formula Hale (6) NH-CO-NH
Halm in which Hal is chlorine or bromine, n and m are 1 or 2 and n + m are 3.

The quaternary ammonium salts are, in particular, those of the formula R

(7) Rio N R8 in which RV R8, and R. and R10, independently of one another, are C1-C18 alkyl, C1-C1Balkoxy or phenyl-Cl-C5alkyl and Hal is chlorine or bromine.

Very especially preferred is the compound of the formula (8) CH2 N (CH2)n-CH3 CI-in which n is a number from 7 to 17.

Monohydric alcohols corresponding to component (a2) or (b4) are linear or branched C2-C.,salcohols, for example ethanol, n-propanol, isopropanol, butanol, lauryl alcohol, cetyl alcohol, 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C9 Cõoxo alcohol, tridecyl alcohol, isotridecyl alcohol or linear primary alcohols ( Alfol types) having 8 to 18 carbon atoms.
Some representatives of these Alfol types are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18).

Other substances which are preferably employed in the liquid formulations according to the invention are monohydric alcohols of the general formula (X) -~) (9) n Y-CH2 OH
in which X is a halogen atom Y is a radical of the formula -O-(CH2)m- or -CH2- or a direct bond;
n is O to 5; and m is 1 to 3.

Preferred compounds of the formula (9) are those in which Y is -O-(CH2)m- and n=0.

x , If dihydric alcohols are employed as component (a2), these have, in particular, 2 to 6 carbon atoms in the alkyl moiety, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,3-, 1,4- or 2,3-butanediol, 1,5-pentanediol and 1,6-hexanediol. 1,2-Propanediol (propylene glycol) is preferred.

Suitable sulfonates (component (b2)) are, in particular, their salts of terpenoids, or mono- or binuclear aromatic compounds, for example sulfonates of camphor, toluene, xylene, cumene or naphthol.

Suitable examples of component (b3) as saturated or unsaturated C3 C12di- or polycarboxylic acids are malonic, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, undecane- and dodecanedicarboxylic acid, fumaric acid, maleic acid, tartaric acid and maleic acid, hydroxyacetic acid (glycolic acid), a-hydroxypropionic acid (lactic acid), and citric and aconitic acid Examples of aliphatic saturated or unsaturated C1-C71monocarboxylic acids are acetic acid, propionic acid, caproic acid, capric acid and undecylenoic acid.
Other suitable substances are aminocarboxylic acids, such as ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetetraacetic acid and nitrilotriacetic acid; cycloaliphatic carboxylic acids, such as campheric acid;
aromatic carboxylic acids, such as benzoic acid, phenylacetic acid, phenoxyacetic acid and zimanic acid, 2-, 3- and 4-hydroxybenzoic acid, anilic acid, and o-, m-and p-chlorophenylacetic acid and o-, m- and p-chlorophenoxyacetic acid;
alkali metal salts and amine salts of inorganic acids, such as the sodium salts, potassium salts and amine(R1R2R3) salts of hydrochloric acid, sulfuric acid, phosphoric acid, C1-C10alkylphosphoric acid and boric acid, R1, R2 and R3 having the abovementioned meanings; isethionic acid; tannic acid; and acid amides of the formula N

(10) /N-CO-R1 in which R1 is hydrogen or C1-C12alkyl and R2 and R3 independently of one another are hydrogen, C1-C12alkyl, C2-C72alkenyl, C1-C12hydroxyalkenyl, C2-C 12hydroxyalkyl, or a polyglycol ether chain having 1 to 30 groups -CH 2 CH2 O- or -CHYI-CHY2 O-, where Y1 or Y2 is one hydrogen radical, the other being methyl, for example N-methyl-acetamide.

All carboxylic acids corresponding to component (b3) which are employed in accordance with the invention can also preferably be employed in the form of their water-soluble alkali metal salts or ammonium salts.

Preferred liquid formulations (a) according to the invention comprise (a) 20 to 70, preferably 30 to 60, % by weight of a microbicidally active ingredient of the formula (1) and (a2) 30 to 80, preferably 40 to 70, % by weight of a mono- or dihydric alcohol or mixtures thereof.

Very especially preferred are formulations which comprise, as component (a2), the compound of the formula (9) as monohydric alcohol, and/or a dihydric alcohol which has 2 to 6 carbon atoms in the alkyl moiety.

Formulations which are preferably employed from amongst the above are formulations which comprise either a monohydric alcohol or a dihydric alcohol.
In particular, a suitable monohydric alcohol is phenoxyethanol and a suitable dihydric alcohol 1,2-propanediol.

Preferred liquid formulations (b) comprise (b1) 10 to 30, preferably 15 to 25, % by weight of a microbicidally active ingredient of the formula (1), (b2) 0 to 80, preferably 10 to 70, % by weight of a sulfonate, (b3) 1 to 60, preferably 10 to 50, % by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid; and (b4) 0 to 90, preferably 5 to 75, % by weight of a mono- or dihydric alcohol, and water to 100%, it always being necessary for one of components (b2) or (b4) to be present.

Very especially preferred liquid formulations (b) are those which comprise cumenesulfonate as component (b2), a hydroxyacid as component (b3) and a dihydric alcohol having 2 to 6 carbon atoms in the alkyl moiety as component (b4)-Mainly of interest are liquid formulations (b) which comprise (b1) 10 to 25% by weight of a microbicidally active ingredient of the formula (1), (b2) 10 to 70% by weight of cumenesulfonate, (b3) 10 to 50% by weight of lactic acid, (b4) 5 to 75% by weight of 1,2-propanediol and water to 100%.

According to a further aspect of the present invention claimed in the parent application, there is provided a concentrated liquid formulation (a) comprising -9a-(a1) 20 to 70% by weight of a microbicidally active ingredient selected from a 2-hydroxydiphenyl ether of the formula YO / Yr (1) z \O (OH)n H
(OH)m in which Y is chlorine or bromine, Z is S02H, N02 or C1-C4alkyl, r is 1 or 2, o is 1 or 2, p is 0, m is 0 and n is 0 or 1, and (a2) 30 to 70% by weight of (i) an alcohol of the general formula (fin (9) \ Y-CH2-OH
in which X is a halogen atom, Y is a radical of the formula -0-CH2- or -CH2- or a direct bond; and -9b-n is 0 or an integer from 1 to 5, or (ii) a dihydric alcohol having an alkyl moiety comprising 2 to 6 carbon atoms.

The liquid formulations according to the invention are used as active ingredient in cosmetic products, for example deodorants, cleansers, lotions/creams, in household articles, for example as an additive in washing-up liquids, liquid household detergents; as an additive in dental care products, for example in mouthwashes or toothpastes, or as an antimicrobially active ingredient for hard and soft surfaces, for example polymers, paper, textiles and, in particular, the human skin.

The liquid formulations according to the invention are furthermore also suitable as preservatives for cosmetic products and household articles.

They are also used as disinfectants for textile fibre materials.

Liquid formulations according to the invention are prepared by dissolving component (a,) or (bl) in component (a2) or (b4), adding the components (b2) and (b3) to the resulting solution, with stirring, making up the resulting solution with deionized water to 90 to 95% of the final volume, if appropriate adjusting the pH with a cosmetically acceptable base, for example mono- or diethanolamine, and making up the mixture with deionized water to an end volume of 100%.

The dissolved microbicidally active ingredient can be incorporated into cosmetic products and household articles in a trouble free manner. The active ingredient, which is pulverulent per se, is offered to the user in dissolved form. Time-consuming predissolving in suitable solvents while supplying heat is no longer required.

Moreover, the liquid formulations according to the invention are distinguished by a synergistic antimicrobial action (see Example 15) and good storage stability.

The examples which follow illustrate the preparation of the liquid formulations according to the invention. Parts are parts by weight.

Preparation examples for concentrated liquid formulations Example 1 60 Parts of the compound of the formula (101) CI -Q- O -p- CI
OH CI

are introduced into a vessel.
40 Parts of 1,2-propanediol are added and the mixture is stirred at 50 to 60 C at medium setting until the compound of the formula (101) is dissolved completely Example 2:
30 Parts of the compound of the formula (101) Cl -Q- O Cl --Q- OH CI

are introduced into a vessel.
70 Parts of 2-phenoxyethanol are added and the mixture is stirred at 50 to 60 C at medium setting until the compound of the formula (101) is dissolved completely.

Example 3:
6 Parts of the compound of the formula (101) and 20 Parts of 1,2-propanediol are weighed into a vessel and stirred at 50 - 60 C at medium setting until a clear solution forms. Then, 30 Parts of citric acid, 35 Parts of sodium xylenesulfonate and 4 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 3 to 4 by adding ethanolamine and the mixture is made up to 100 parts with deionized water.

1 l VN ~N

Example 4:
15 Parts of the compound of the formula (101) and Parts of ethanol are weighed into a vessel and stirred at room temperature until a clear solution forms. Then, 35 Parts of undecylenoic acid Parts of sodium xylenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 3 to 4 by adding ethanolamine and the mixture is made up to 100 parts with deionized water.

Example 5:
10 Parts of the compound of the formula (101) and 5 Parts of 1,2-propanediol are weighed into a vessel and stirred at room temperature.
Parts of tartaric acid are added. The pH is then brought to 3 to 4 by adding ethanolamine.
30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The mixture is made up to 100 parts with deionized water.

Example 6:
10 Parts of the compound of the formula (101) and 5 Parts of 1,2-propanediol are weighed into a vessel and stirred at room temperature.
Parts of lactic acid are added. The pH is then brought to 3 to 4 by adding ethanolamine.
30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The mixture is made up to 100 parts with deionized water.

Example 7:
Parts of the compound of the formula (101) and 10 Parts of 1,3-butanediol are weighed into a vessel and stirred at room temperature until a clear solution forms. Then, 30 Parts of tartaric acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 3 to 4 by adding ethanolamine. The mixture is made up to 100 parts with deionized water.

Examples 8 to 13: Other liquid formulations with alternative microbicidally active ingredients Example 8 10 Parts of benzyl alcohol and 5 Parts of propylene glycol are weighed into a vessel and stirred at room temperature. Then, 40 Parts of lactic acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding monoethanolamine, and the mixture is made up to 100 parts with deionized water.

Example 9 Parts of 2,4-dichlorobenzyl alcohol and 5 Parts of propylene glycol are weighed into a vessel and stirred at room temperature until a clear solution forms. Then, 40 Parts of lactic acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding monoethanolamine, and the mixture is made up to 100 parts with deionized water.

Example 10:
10 Parts of p-chloro-m-xylenol, 5 Parts of propylene glycol and 30 Parts of sodium cumenesulfonate are weighed into a vessel and stirred at room temperature until a clear solution forms. Then, 40 Parts of lactic acid and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding ethanolamine, and the mixture is made up to 100 parts with deionized water.
Example 11:
10 Parts of o-phenylphenol and 5 Parts of propylene glycol are weighed into a vessel and stirred at 50-60 C at medium setting until a clear solution forms. Then, 40 Parts of lactic acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is 1. 1..M.

continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding monoethanolamine, and the mixture is made up to 100 parts with deionized water.

Example 12:
Parts of p-chloro-m-cresol and 5 Parts of propylene glycol are weighed into a vessel and stirred at 50-60 C at medium setting until a clear solution forms. Then, 40 Parts of lactic acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding ethanolamine, and the mixture is made .up to 100 parts with deionized water.

Example 13:
10 Parts of benzalkonium chloride and 5 Parts of propylene glycol are weighed into a vessel and stirred at room temperature until a clear solution forms. Then, 40 Parts of lactic acid, 30 Parts of sodium cumenesulfonate and 10 Parts of deionized water are added in the above sequence and stirring is continued until all constituents are dissolved. The pH of the mixture is brought to 5.5 by adding monoethanolamine, and the mixture is made up to 100 parts with deionized water.

Example 14: Detection of the microbicidal activity in the suspension test Test Staphylococcus aureus ATCC 9144 microorgan- Enterococcus faecium ATCC 10541 isms Escherichia coli ATCC 10536 Pseudomonas aeruginosa CIP A-22 Candida albicans ATCC 10231 Nutrient Casein soy flour peptone broth for growing the inoculum media: Casein soy flour peptone agar with 3% polyoxyethylene(20)sorbitanmono-oleate; 0.3% lecithin; 0.1% L-histidine Dilution Trypticase soy flour peptone broth with 10%
polyoxyethylene(20)sorbitan-medium: monooleate, 3% lecithin; 0.1% L-histidine and 0.5% sodium thiosulfate.

a. Use of the formulation of Example 6 as disinfectant These tests show that the liquid formulations according to the invention have a very potent microbicidal activity, even at low concentrations. These properties are important for disinfectants in general, but in particular for the disinfection of textiles.

Procedure:
0.1 ml of the formulation of Example 6 is diluted with 8.9 ml of water and the dilution is subsequently treated with 1 ml of a 1:10 dilution of a culture of the test bacteria which is incubated for 16 to 24 hours at 37 C (= 1% of the formulation of Example 6).
The concentration of the test organisms in the batch is 108 microorganisms/ml.
The batch is mixed thoroughly and subsequently incubated for 5 minutes at room temperature with gentle stirring.
After 5 minutes, 1 ml of the batch is removed and the live bacterial count is determined. To this end, dilutions are performed in dilution medium, and 0.1 ml each of these dilutions are plated onto agar media.

The live bacterial count is determined after the plates have been incubated for 24 to 48 hours at 37 C by counting the colonies taking into consideration the dilution factor.

The test results are shown in Table 1.

Table 1 Batch Reduction in bacterial count after 5 minutes (log) S. aureus ATCC Ent. faecium E. coli ATCC P. aeruginosa Water 0 0 0 0 1% Formulation 6 >10 > 10, > 10 > 105 The tested formulation of Example 6 shows a reduction of all test microorganisms by at least 5 powers of ten after as little as 5 minutes in the suspension test.

b. Liquid soap with a concentrated formulation comprising 2,4,4'-trichloro-2'-hydroxydiphenyl ether The tests of Examples 14b. and 14c. show that soap formulations to which the liquid formulations according to the invention are added have a powerful microbicidal activity, which is required for use as a disinfectant or decontaminant for hands, but also for the microbicidal treatment of surfaces (surface disinfectants, antimicrobial dishwashing products, household detergents and the like).

Test formulation:
4% of sodium lauryl sulfate 10% of formulation of Example 6 to 100% water The pH is brought to 5.5 using ethanolamine.
Procedure:
9 ml of the formulation are mixed with 1 ml of a 1:10 dilution of a bacterial suspension which has been incubated at 37 C for 16 to 24 hours, and the mixture is subsequently incubated at room temperature with stirring.
After an incubation time of 30 seconds, 1 ml of the test batch is removed, diluted in dilution medium, and 0.1 ml each of the dilutions are plated onto agar media.
After the plates have been incubated for 24 to 48 hours at 37 C, the live microbial count is determined by counting the colonies taking into consideration the dilution factor.

''1 11,1111-1 The test results are shown in Table 2.
Table .2:

Test microorganism Reduction of test microorganisms after 30 seconds (Log) S. aureus ATCC 9144 > 5 E. faecium ATCC 10541 > 5 E. coli ATCC 10536 > 5 P. aeruginosa CIP A-22 > 5 S. marcescens ATCC 13880 2.2 C. albicans ATCC 10231 2.4 The liquid soap shows a very powerful microbicidal activity against the microorganisms tested.

c. Liquid soaps with concentrated formulations:
Test formulations:
Soaps of the following compositions are tested:
4% of sodium lauryl sulfate, 10% of concentrated formulation of Examples 9 to 14, to 100% water The pH is brought to 5.5 using monoethanolamine.
Procedure:
9 ml of the formulation are mixed with 1 ml of a 1:10 dilution of a bacterial suspension which has been incubated at 37 C for 16 to 24 hours, and the mixture is subsequently incubated at room temperature with stirring.
After an incubation time of 1 minute, 1 ml of the test batch is removed, diluted in dilution medium, and 0.1 ml each of the dilutions are plated onto agar media.
After the plates have been incubated for 24 to 48 hours at 37 C, the live microbial count is determined by counting the colonies taking into consideration the dilution factor.

The test results are shown in Table 3:

Table 3 Test soap with concentrated Reduction of test microorganisms after 1 formulation of Example minute (log) P. aeruginosa CIP A-22 9 >5 >5 11 >5 12 >5 13 >5 14 >5 Placebo 0.9 All formulations tested show a potent bactericidal activity.

Example 15: Preservative stress tests with liquid soaps Repetitive preservative stress tests (triple stress) demonstrate that the concentrates are highly suitable for the preservation of cosmetics and household articles.

Soap formulation:
6% of sodium laureth-2 sulfate, to 10O% water The pH is brought to 5.5 with monoethanolamine.

The soap formulation is preserved with the following concentrated formulations:
A: 3% of the formulation of Example 7 B: 10% of the formulation of Example 2 Test micro- Staphylococcus aureus ATCC 9144 organisms Escherichia coli ATCC 10536 Enterobacter gergoviae ATCC 33028 Klebsiella oxytoca DSM 30106 Pseudomonas aeruginosa CIP A-22 Pseudomonas fluorescens ATCC 17397 Candida albicans ATCC 10231 Aspergillus niger ATCC 6275 Nutrient Casein soy flour peptone agar with 3% polyoxyethylene(20)sorbitanmono-media oleate; 0.3% lecithin; 0.1 % L-histidin for bacteria and yeasts Dilution Trypticase soy flour peptone broth with 10% polyoxyethylene(20)-medium: sorbitanmonooleate; 3% lecithin; 0.1% L-histidine and 0.5% sodium thiosulfate.

Procedure:
20 g of the soap formulation in question are inoculated with 0.2 ml of a microorganism suspension in such a way that the resulting microbial stress of the product is 105 to 106 microorganisms/g of product.

In order to determine the total microbial count at a particular point in time, 1 g of material is removed, and a dilution series is established in dilution medium. The total microbial count is determined by plating 0.1 ml of the dilutions onto agar media after incubation at 37 C for 24 hours (bacteria and yeasts) or incubation at 28 C for 5 days (Aspergillus).

The total bacterial count in the product is determined after inoculation and also after 1 and 2 weeks. After 2 and 4 weeks, the product is again inoculated in the same manner with test microorganisms, and the total microbial counts are determined after a further 1 and 2 weeks in each case.

The test results are shown in Table 4:
Table 4:
Test microorganisms Preservation A B Unpreserved " 29276-740D

S. aureus ATCC 9144 +/+/+ +/+/+ -/-/-E. coli ATCC 10536 +/+/+ +1+/+ -/-/-Ent. gergoviae ATCC 33028 +/+/+ +/+/+ -/-/-Ps. aeruginosa CIP A-22 +/+/+ +/+/+ -1-1-Ps. fluorescens ATCC 17397 +/+/+ +/+/+ -/-/-C. albicans ATCC 10231 +/+/+ +/+/+ -/-/-Aspergillus niger ATCC 6275 +/+/+ +/+/+ -/-/-+ = Reduction of total bacterial count of at least 99% in the course of 2 weeks after an inoculation.
- = Reduction of total microbial count of less 99% in the course of 2 weeks after an inoculation.

Example 16: Preparation of a syndet (detergent formulation):
15.7% of alkylarylsulfonate 3.7% of fatty alcohol sulfonate 2.7% of fatty acid monoethanolamide 39% of tripolyphosphate 4% of sodium silicate 2% of magnesium silicate 1% of carboxymethylcellulose 0.5% of EDTA
2% of the formulation of Example 2 4.7% of water Preparation:
The ingredients are stirred with equivalent amounts of water to a slurry. The resultant paste is dried at 50 C and finally pressed through a sieve with a mesh diameter of 0.8 mm.
Particles <0.3 mm are discarded.

Example 17: Preparation of a dishwashing product 7% of sodium lauryl sulfate 7% of sodium myreth sulfate 4% of lauryl glucoside 1% of cocamidopropylbetaine 1% of the formulation of Example 6 1% of sodium chloride 0.02% of dibromodicyanobutane 0.08% of phenoxyethanol 78.9% of water Preparation:
Sodium lauryl sulfate are mixed with sodium myreth sulfate and lauryl glucoside and solved in 30 parts of water. The formulation of Example 6 is added and homogenized.
Cocamido-propylbetaine, sodium chloride, dibromodicyanobutane and phenoxyethanol are added.
The pH is adjusted to 6.0 with citric acid. Water is added to give 100 parts.

Example 18: Preparation of a disinfectant for textiles:
50% of the formulation of Example 6 10% of lauryl alcohol polyglycol ether to 100% of water The pH is brought to 5 with monoethanolamine Example 19: Preparation of a hand disinfectant 4% of sodium lauryl sulfate 0.5% of hydroxyethylcellulose 3% of the formulation of Example 2 to 100% of water Preparation:
Sodium lauryl sulfate are dissolved in 20 parts of water, the formulation of Example 2 is added. Hydroxyethylcellulose is dissolved in 60 parts of water at 60 C, cooled down and added to the surfactant mixture. The pH is adjusted to 5.5 with monoethanolamine. Water is added to give 100 parts.

Example 20: Preparation of a hand disinfectant 4% of sodium lauryl sulfate 0.5% of hydroxyethylcellulose 10% of the formulation of Example 7 to 100% of water The pH is brought to 5.5 with monoethanolamine Preparation:
Sodium lauryl sulfate are dissolved in 20 parts of water, the formulation of Example 2 is added. Hydroxyethylcellulose is dissolved in 60 parts of water at 60 C, cooled down and added to the surfactant mixture. The pH is adjusted to 5.5 with monoethanolamine. Water is added to give 100 parts.

Example 21: Preparation of a shower gel 6% of sodium laureth-2 sulfate 3% of cocamidopropylbetaine 1.5% of hydrolysed protein 1.5% of laureth-9 0.3% of polyquaternium-7 1% of the liquid formulation of Example 2 1.0% of glycol distearate 0.2% of sodium chloride to 100% of water Preparation:
Glycol distearate is dissolved in sodium laureth-2 sulfate at 50 C. The remaining ingredients and 30 parts of water are added in succession and homogenized.
The pH is adjusted to 5.5 with monoethanolamine and water is added to give 100 parts.
Instead of 1 % of the formulation of Example 2, it is also possible to employ 0.5-1.5% of the formulation of Example 1 or 1-10% of the formulation of Examples 3 to 12.

Claims (11)

1. A concentrated liquid formulation (b) comprising (b1) 5.1 to 30% by weight of a microbicidally active ingredient which is a 2-hydroxydiphenyl ether of the formula (1) in which Y is chlorine or bromine, Z is SO2H, NO2 or C1-C4alkyl, r is 0 to 3, o is 0 to 3, p is 0 or 1, m is 0 or 1 and n is 0 or 1;

(b2) 0 to 80% by weight of a sulfonate;

(b3) 1 to 60% by weight of a C1-C11monocarboxylic acid or of a C3-C12di- or -polycarboxylic acid;

(b4) 0 to 90% by weight of a mono- or dihydric alcohol or mixtures thereof; and water to 100%, it always being necessary for one of the components (b2) or (b4) to be present.

2. A liquid formulation according to claim 1, which comprises 10 to 30% by weight of the microbicidally active ingredient.

3. A concentrated liquid formulation (b) according to claim 1 comprising (b1) 10 to 25% by weight of the microbicidally active ingredient;

(b2) 10 to 70% by weight of cumenesulfonate;
(b3) 10 to 50% by weight of lactic acid;

(b4) 5 to 75% by weight of 1,2-propanediol, and water to 100%.

4. A liquid formulation according to claim 3, wherein component (b1) has the formula .

5. The use of a liquid formulation according to any one of claims 1 to 4 as antimicrobially active ingredient in cosmetic products.

6. The use of a liquid formulation according to any one of claims 1 to 4 as antimicrobially active ingredient in household articles.

7. The non-therapeutic use of a liquid formulation according to any one of claims 1 to 4 as antimicrobially active ingredient for hard and soft surfaces.

8. The non-therapeutic use according to claim 7, wherein the liquid formulations are used for human skin.

9. The use of a liquid formulation according to claims 1 to 4 as a preservative in cosmetic products and household articles.

10. The use of a liquid formulation according to claims 1 to 4 as disinfectant for textiles.

11. The non-therapeutic use of a liquid formulation according to claims 1 to 4 as decontamination agent or disinfectant for the skin and hard surfaces.