WO1998049898A1

WO1998049898A1 - Novel biocidal agents comprising quarternary bisimidazoline surfactants

Info

Publication number: WO1998049898A1
Application number: PCT/US1998/009302
Authority: WO
Inventors: Ji Li; Manilal S. Dahanayake; Robert Lee Reierson; David James Tracy
Original assignee: Rhodia Inc.
Priority date: 1997-05-09
Filing date: 1998-05-05
Publication date: 1998-11-12
Also published as: AU7372098A

Abstract

Novel biocidal agents are comprised of a new class of quaternary cationic surfactants having two imidazolinium groups comprising compounds of formula (I) wherein surfactants have two hydrophobic moieties and two hydrophilic groups per molecule and are useful as disinfectants and in other anti-microbial compositions.

Description

NOVEL BIOCIDAL AGENTS COMPRISING QUATERNARY BISIMIDAZOLINE SURFACTANTS

FIELD OF THE INVENTION

The invention relates generally to anti-microbial compositions and their use as disinfectants.

BACKGROUND OF THE INVENTION

Long chain non-aromatic quaternary ammonium compounds in addition to their aggregative properties, solubilizing properties, and surface tension reducing properties, have long been used for their anti-microbial effects upon various strains of microorganisms. (E. Jungermann; Cationic Surfactants;

Surfactant Science Series; Vol. 4: 1970).

Devinsky (Tenside Detergents 22, 10 (1985)) has recently described

the influence of surfactant structure upon the critical micelle concentration

(cmc) and the antimicrobial activity expressed as the minimum inhibitory

concentration (mic). A correlation was found between cmc and mic indicating

the optimum activity is demonstrated by quaternary imidazoline surfactants

exhibiting a cmc between about 10^"2 and 10^" M.

Certain quaternary imidazoline surfactants have been discovered that

have lower cmc values yet exhibit unexpected exceptional anti-microbial

activity. It is highly desirable to employ quaternary surfactants at very low levels (i.e., materials with low mic's) in order to minimize the quantities of toxic materials in the environment. Generally, the manufacture of imidazoline compounds involves the reaction of a polyamine containing a secondary amine group in a gamma

position with respect to at least one primary amine group with a carboxylic acid or ester Following the initial condensation, namely amide formation, the intermediate is cychzed in a second stage to the imidazoline structure

Bisimidazoline quaternary surfactants are relatively unknown in the art

U S Patent Nos 3,887,476 and 3,855,235 to McConnell disclose the

preparation of bisimidazoline derivatives as fabric softeners U S Patent No

3,244,724 to Guttman also teaches the use of bisimidazohnes as sulfoalkylated quaternary surfactants for use as fabric softeners

United States Patent No 5,569,767 to Uphues et al teaches a class of storage stable ampholytic surfactants consisting of 1 -hydroxyethyl-2-alkyl-2- imidazohnes which are quaternated or carboxymethylated with halogenated

carboxylic acid salts at a pH of 7 5 to 9 0 The surfactants are asserted to be

useful in dishwashing detergents, cosmetics and personal care products

None of these patents or other prior art recognizes the unexpected biocidal activity of these compounds

SUMMARY OF THE INVENTION

A class of quaternary cationic surfactants that exhibit superior anti-

microbial activity have been provided The compounds of the invention comprise compounds of the formula

wherein R can independently represent alkyl, hydroxy-substituted or perfluorinated alkyl of from about 5 to about 22 carbon atoms; R₂ can be alkylene or alkylaryl of about 1 to about 10 carbon atoms and the hydroxy-substituted derivatives thereof or R₃ - D - R₃ wherein R₃ can independently be alkylene of

from about 1 to 6 carbon atoms and the hydroxy-substituted derivatives thereof as

well as aryl, and D represents -0-, -S-, -S0₂-, a polyether group [-O(R O)_x-], aryl or

wherein A is R₅C(0)- (acyl) or H and R₅ is a C₅ to C₂₂ straight or branched-

chain alkyl, R₆ is a Ci to C₆ alkyl and the hydroxy-substituted derivatives thereof, n is an integer of 1 to 4 inclusive, X being a whole number between about 1 and 20

where R₄ represents C₂ to C₄ alkyl or alkyl and X is a Ci to Cιo alkyl or alkylaryl and their hydroxy-substituted derivatives thereof and Y is an anion.

DETAILED DESCRIPTION OF THE INVENTION While the compounds of the invention can be prepared by a variety of synthetic routes, it has been found that they can be produced particularly effectively by quaternizing a bisimidazoline prepared by a novel process disclosed and claimed in copending application "Amphoteric Surfactants having Multiple Hydrophobic and Hydrophilic Groups", U.S.S.N. 08/292,896 filed on August 19, 1994 that is hereby incorporated by reference. There a polyamine reactant having at least four amino groups, of which two are terminal primary amine groups, is reacted with an acylating agent such as a carboxylic acid, ester, and the naturally occurring triglyceride esters thereof or acid chlorides thereof in an amount sufficient to provide at least about 1.8 fatty acid groups (R^O)-) per polyamine to provide a bisimidazoline of the formula:

This reaction proceeds effectively at elevated temperatures (about 100°C -

250°C) with continuous removal, such as by distillation, of the resulting condensate (H₂0) during the course of the reaction.

The progress of the reaction can be monitored by the amount of water

recovered in the distillate. Two moles of water are generated for each imidazoline

ring formed, one mole in the condensation reaction and one mole in the cyclodehydration reaction to form the imidazoline. Hence, these amounts should be doubled for the bisimidazoline compounds of the invention. The process can

be carried out with or without a catalyst, at atmospheric, reduced or super

atmospheric pressure. The use of excess amine can result in undesirable by- products and is not recommended. Stoichiometric excess of fatty acid, ester, chloride or triglyceride can be used but is less desirable as it may require a purification step to remove the excess.

In the compounds of Formula I and II, R can be derived from fatty acids, esters and triglycerides or the acid chlorides thereof from synthetic and natural sources which will generally contain mixtures of different carbon chain length

saturated and unsaturated aliphatic radicals. The natural sources can be coconut

oil (preferred) or similar natural oil sources such as palm kernel oil, palm oil, soya oil, rapeseed oil, castor oil or animal fat sources such as herring oil and beef tallow. Generally, the fatty acids from natural sources in the form of the fatty acid

or the triglyceride oil can be a mixture of alkyl radicals containing from about 5 to about 22 carbon atoms. In a more preferred material, the mixture of alkyl radicals can be derived from a saturated portion of coconut oil (from about 6 to about 18 carbon atoms) or similar natural vegetable oils. These ranges cover about 90% of the carbon chains in the compound. Since these fatty acids are derived from

natural sources, they may also contain small amounts of other carbon chains.

Illustrative of the fatty acids in these oils are caprylic (C₈), capric (Cι₀), lauric (Cι₂),

myristic (Cι₄), palmitic (Cι₆), stearic (Cι₈), oleic (Cι₈, mono-unsaturated), linoleic

(Ci_δ, di-unsaturated), linolenic (Cι₈, tri-unsaturated), ricinoleic (Cι₈, mono- unsaturated), arachidic (C₂₀), gadolic (C₂₀, mono-unsaturated), behenic (C₂₂) and

erucic (C₂₂). These fatty acids can be used per se, as concentrated cuts or as fractionations of natural source acids. The fatty acids with even numbered carbon chain lengths are preferred, although the odd numbered fatty acids can also be

used. In addition, single carboxylic acids such as lauric acid, or others as determined by the particular application, may be used. Examples of acids derived

from synthetic sources that can be used include 2-ethylhexanoic acid, pelargonic acid as well as acids derived from Guerbet and similar alcohols.

The polyamine reactant has at least four amino groups of which two are terminal primary amine groups. The preferred polyamine is triethylenetetramine

(TETA). Other polyamines such as tetraethylenepentamine that would be obvious to one of skill in the art can also be used. The amine reactant can be

defined by the structure:

III. H₂NCH₂CH₂NH - R₂ - NHCH₂CH₂NH₂

wherein R₂ is generally alkyl or aminoalkyl. The improved method of the invention will be illustrated with TETA but this is not intended to limit the invention

to that starting material. TETA is reacted with a sufficient amount of fatty acid to provide at least about 1.8 fatty acid groups, preferably from about 1.9 to about 2.5 fatty acid

groups, per molecule of polyamine to provide the bisimidazoline compound of the

invention as in Formula I wherein R₂ is ethylene.

A second mode of synthesis of the bisimidazoline includes the steps of

forming a single imidazoline such as that formed by the reaction of

ethylenediamine and a fatty acid, ester, chloride or triglyceride. The fatty acids,

esters, chlorides or triglycerides thereof can be reacted with α-, and β- diamines

in substantially equimolar quantities at temperatures ranging from about 150° to

250°C with continuous removal of the resulting condensate (H₂O). The process can be carried out with excess amine, with or without a catalyst, at atmospheric, reduced or super atmospheric pressure.

The imidazoline can then be reacted with any difunctional compound that

will join two of the imidazoline rings to form the bisimidazoline compound of the

invention. These can be illustrated by any reactive dihalide, e.g., alpha, omega- dihalobutane, alpha, beta-dihaloethane, alpha, alpha'-dihaloparaxylene, diglycidyl ethers, diepoxides as well as epihalohydrins such as epichlorohydrin and the like.

In addition to the alkyl and aminoalkyl groups contained in the examples of

the poylamines given above, R₂ can also represent hydroxy-substituted alkyl such

as -CH₂CHOHCH-₂; an ether such as -CH₂CH₂OCH₂CH₂- or an alkylarylalkyl such as -CH₂-C₆H₄-CH₂-.

For reaction conditions generally, see F. Linsker and R. Evans JACS 67, 1581 (1945); C. K. Ingold and E. Rothstein, JCS 1666 (1931 ), the disclosures of which are incorporated herein by reference. The reaction conditions must be

such as to maintain the imidazoline ring structures.

The novel quaternary surfactants that comprise the biocidal compositions

of the present invention can be prepared by reacting the bisimidazoline with an

alkylating agent as is known in the art. The alkylating agent employed can be

anyone of a number of known agents, for example the alkyl halides such as methylchloride, butylbromide, ethylbromide, and hexadecyl chloride; alkyl sulfates

such as dimethylsulfate, diethylsulfate as well as aryl chlorides such as benzyl

chloride, chlorobenzyl chloride, dichlorobenzyl chloride, and ethyl chloride, with

dimethylsulfate being preferred. In Formula I, Y is an anion associated with the

alkylating agent, representative anions including chloride, methylsulfate, ethylsulfate, and the like. Equimolar quantities of the alkylating agent per imidazoline ring can be used but a slight excess of the alkylating agent is preferred to assure maximum quatemization. The excess of the alkylating agent

is desirably sufficient to effect a pH in the reaction medium of from about 5 to about 7. The reaction temperature is preferably in a range of from about 40° to about 80°C. and from 1 to about 12 hours will be necessary to complete the

reaction.

The surfactants of the invention can exhibit extremely low critical micelle concentrations (cmc) as compared with conventional surface-active agents because of the presence of two hydrophobic chains and two hydrophilic groups in the molecule. In addition, they are able to significantly reduce surface tension and are highly soluble in water. By virtue of these characteristics and their anti¬

microbial properties, the surfactants of the present invention provide the active ingredient for superior disinfectant and bactericidal compositions. While the surfactants of the invention can be used alone as the essential hydrotrope component, blends of the compounds of the invention with

certain conventional well known anionic, nonionic, cationic and amphoteric

surfactants can provide improved results beyond that expected which can be

shown by the critical micelle concentration and the surface tension reducing ability of the blends.

Examples of the nonionic surfactants useful as blends herein include fatty

acid glycerine esters, sorbitan fatty acid esters, sucrose fatty acid esters,

polyglycerine fatty acid esters, higher alcohol ethylene oxide adducts, single long

chain polyoxyethylene alkyl ethers, polyoxyethylene alkylallyl ethers, polyoxyethylene lanolin alcohol, polyoxyethylene fatty acid esters, polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidones, glucamides, alkylpolyglucosides, mono- and dialkanol amides, polyoxyethylene alcohols, mono- or diamides and alkylamine oxides.

Examples of the anionic surfactants useful as blends herein include fatty

acid soaps, ether carboxylic acids and salts thereof, alkane sulfonate salts, α-

olefin sulfonate salts, sulfonate salts of higher fatty acid esters, higher alcohol sulfate ester salts, fatty alcohol ether sulfate salts, higher alcohol phosphate ester salts, fatty alcohol ether phosphate ester salts, condensates of higher fatty acids and amino acids, and collagen hydrolysate derivatives. Examples of the cationic surfactants useful herein include alkyltrimethylammonium salts, dialkyl- dimethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylisoquinolinium salts, benzethonium chlorides, and acylamino acid-type

cationic surfactants.

Examples of the amphoteric surfactants useful as blends herein include

amino acids, betaines, sultaines, phosphobetaines, imidazoline-type amphoteric

surfactants, soybean phospholipids, and yolk lecithins.

In addition to the foregoing surfactants, any of commonly used auxiliary

additives may be added to the surfactants of the invention or blends thereof with

other surfactants as disclosed herein. Such auxiliary additives may be added to the surfactants of the invention just before or during use. Such auxiliary additives may be suitably chosen for the desired composition and will generally include inorganic salts such as Glauber salt and common salt, builders, humectants, solubilizing agents, ultraviolet (UV) light absorbers, softeners, chelating agents, and viscosity modifiers. The quaternary cationic surfactant compositions are particularly useful as

biocidal agents in disinfectant compositions, industrial and household cleaners, dish and laundry detergents and the like.

The following examples are disclosed for illustrative purposes only in order to better describe and disclose how to specifically practice and carry out the claimed invention. It is recognized that minor changes and variations may be made with respect to the compositions and their formulations that are not disclosed therein. It is to be understood then that to the extent any such changes do not materially effect the final products and their end use, such changes or variations therefrom are contemplated as falling within the spirit and scope of the invention as recited in the claims that follow.

Example 1

The preparation of:

(A) Bisimidazoline

To a 500 milliliter (ml.) three-necked round bottom flask equipped with a

stirrer, temperature controller, and a Barrett distilling receiver with a condenser on

top were added 46.7 grams (0.25 mol) triethylene tetramine hydrate (average 2J

to 2.2 moles water by Karl Fisher Analysis), 104 gms (0.52 mol) lauric acid and

100 mis. toluene. The Barrett distilling receiver was filled with toluene. The

reaction mixture was gently heated with stirring to the boiling point of the toluene

(120° - 130° C) at which point water collection was initiated.

The amount of water that azeotroped with the toluene was determined.

The first 20 mis. which was collected in the first 3 hours of reaction indicated that the reaction was 70% complete. Water collection was continued, and the reaction temperature was slowly raised to 160° - 180°C during the 12th to 16th hour of reaction by releasing reactor-contained toluene from the Barrett distilling receiver. The progress of the reaction was also determined by gas chromatography. The disappearance of peaks corresponding to mono- and di- amides indicated completion of the condensation reaction.

After 16 hours of reaction, the reaction was stopped while 27.2 mis. (28 mis. calculated) of water had been collected. Gas chromatography showed that the 126 grams of product obtained contained greater than 96% of bis-imidazoline.

The product was recrystallized from CHCI₃ for structure characterization

and identification. ¹H- and ¹³C-NMR, IR, and mass spectra were recorded and the results obtained showing the formation of ethylene bislaurimidazoline which agreed with the postulated structure.

(B) Quatemization

Ethylene bislaurimidazoline as prepared in Step A and dimethyl

sulfate were mixed in a 1 :2 molar ratio and added to a 250 milliliter three-necked

round bottom flask equipped with magnetic stirrer, temperature control and a condenser. The solvent of choice is listed in Table I. The reaction mixture was

heated to 50-75°C for 8 to 10 hours. An oily liquid was obtained which was very

water soluble and exhibited good wetting and foaming properties. ¹H- and ¹³C-

NMR and IR characterizations confirm the structure in the above formula. The parameters and results are shown in Table #1 : TABLE 1

STARTING MATERIALS REACTION CONDITIONS

Example 2

Preparation of:

I

CH₂

(A) Bisimidazoline

To a 500 milliliter three-necked flask were added 46.7 g (0.25M)

triethylenetetramine hydrate, 108.2 g (0.52 mole) coconut fatty acid and 100 ml toluene. The reaction mixture was heated to 120°-130°C and water

azeotroped. The reaction temperature was raised to 160°C to complete the

reaction and remove toluene. The resulting bisimidazoline product was

analyzed by gas chromatography and NMR and both spectra confirmed the

expected structure of the composition. (B) Quaternization

To a 250 ml. flask was charged the bisimidazoline prepared above and dimethylsulfate in a 2:1 molar ratio in toluene. The reaction mixture was

heated to 75°C and held overnight. The toluene was stripped, yielding the

bisquaternary imidazoline surfactant compound set forth above.

Example 3

Preparation of:

(A) Bisimidazoline

To a flask was added 46.7 g (0.25 M) triethylenetetramine hydrate,

139.4 g (0.52M) triple-pressed stearic acid and 100 ml toluene. The reaction

was heated to 120°-130°C to azeotrope the water. The reaction temperature

was raised to 190°C in order to remove the water and toluene. The resulting bisimidazoline was analyzed by NMR and its structure confirmed.

(B) Quaternization

To a round bottom flask was added 231 g (0.37M) bisimidazoline and

94.5 g (0.75 M) dimethylsulfate and 91 g of isopropyl alcohol. The reaction

was heated to 70°C-75°C and held overnight. ¹H and ¹³CNMR analysis confirmemd the formation of the quaternary bisimidazoline compound.

Example 4

Preparation of: CH₃

(A) Bisimidazoline

To a flask was added 46.7 g (0.25M) triethylene tetramine hydrate, 133.7 g (0.52M), palmitic acid and 100 ml toluene. Water was azeotroped off and toluene stripped, yielding the bisimidazoline.

(B) Quaternization

To 219 g (0.37M) imidazoline in 95 g isopropanol was added 94.5 g

(0.75M) dimethylsulfate. The reaction was heated to 75°C and held overnight.

The quaternary bisimidazoline surfactant was analyzed and its structure

confirmed by NMR. Example 5

(A) Quaternization

To 185 gms. of bis-cocoimidazoline (prepared in step A of example 2) was added 100 gms. isopropanol. The reaction mixture was heated to 75°C

and 100 g of butylbromide was added. Analysis by sodium bromide titration indicated the complete reaction had taken place.

Example 6

Surface Properties

The surfactants of the invention were measured for critical micelle concentration (cmc) and their ability to reduce surface tension as a direct indication of biocidal activity.

The test methods utilized are described as follows: Critical Micelle Concentration (CMC)

Aqueous solutions of the surfactant synthesized according to example

1 to 5 were prepared at varying concentrations. The surface tension at 20°C

was measured by the Wilhelmy plate method and plotted vs. the logarithm of the concentration. The critical micelle concentration was determined as the

value at which the slope of the line changed abruptly. Surface Tension Reducing Ability (gamma CMC)

The surface tension reducing ability was determined as a function of

the surface tension at the critical micelle concentration.

Surface tension measurements were made for each of the surfactants

synthesized in examples 1 -5 using a Kruss K-12 Tensiometer (plate method). Each experiment was carried out as follows:

Distilled water solutions at different concentrations were prepared for

each of the test surfactants in 100 ml amounts. The mixtures were stirred until homogeneous solutions were obtained. The surface tensions of these solutions were then measured.

From the surface tension data, the area/molecule (area) at the interface and efficiency of adsorption were computed by use of the appropriate Gibb's Adsorption Equation:

logC where

p = surface excess concentration (mol/cm²)

dγ = change in surface or interfacial tension of the solvent (dyn«cm^"1)

R = 8.31x10⁷ erg mol^"1. K^~1

C = molar concentration of solution

T = absolute temperature (°K)

pC-20 at the solution/air interface is defined as the negative logarithm of the surfactant concentration required to lower surface tension by 20

dyne/cm.

The results obtained for the surfactants alone are reported in Table 1.

TABLE 2

Example 7 - Minimum Inhibitory Concentration

Minimum inhibiting concentrations (mic) were determined using the

method of Sahm, D. F. and J. A. Washington; Manual of Clinical Microbiology 5th ed., 1991. American Soc. Microbiology, Washington, D.C.

Stocks of each test material 1 % (wt./vol.) were prepared in sterile

Mueller-Hinton broth. Six-fold 1 :10 serial dilutions of each 1 % stock were placed into sterile Mueller-Hinton broth (0.01 through 10,000 ppm) divided out as 1 ml aliquots of each concentration were distributed into sterile capped

polypropylene culture tubes. A 10⁵ cfu/ml inoculum of each bacterial organism was prepared from a 10⁸ cfu/ml culture stock. Microbial species used included Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginoso, Asperqillus niger, Chlostridium albicans. Yeast and mold organisms yield was

approximately 10⁵ cfu/ml inoculum. Each serial dilution of the test material was inoculated (in duplicate) with 1.0 ml of the appropriate test organism. The

addition of the 1 ml aliquot of test organism to the 1 ml aliquot of test material dilutes the effective dose of test material concentration by one-half. The

inoculated media were then incubated at 35°C for 48 hrs. The mic is the

lowest concentration which inhibits the growth of each organism. No growth

is shown by the presence of a clear fluid in the tube and the absence of a

pellet of cells in the tube bottom or the broth's surface, thereby indicating

highly effective biocidal activity.

The biocidal activity of the surfactants was determined to be as follows: TEST ORGANISM (ppm)

The standard is dodecyl-trimethylammonium bromide.

The results indicate compounds of the invention show surprisingly superior anti-microbial activity compared to a standard quaternary ammonium surfactant, dodecyl- trimethylammonium bromide. Much lower quantities of the compound are needed for biocidal activity. Secondly, activity is extremely high even though cmc values are considerably lower than 10^"4. Generally,

these compounds would not be expected to exhibit such high kill rates.

Claims

What is claimed is:

1. A biocidal agent consisting essentially of a surfactant comprising compounds of the formula:

wherein Ri can independently be alkyl, hydroxy-substituted or perfluorinated alkyl of from about 5 to about 22 carbon atoms; R₂ can be alkylene or alkylaryl of 1 to about 10 carbon atoms and the hydroxy- substituted derivatives thereof or R₃ - D - R₃ wherein R₃ can independently be alkylene of from 1 to about 6 carbon atoms and the hydroxy-substituted derivatives thereof as well as aryl, and D represents - 0 - , - S -, - S0₂ -,

a carbonyl group, a polyether group [-O(R₄-O)_x-], or

or aryl wherein R₄ represents a C₂-C₄ alkyl, and A represents R₅ C(O) or H and, R₅ independently represents about C₅ to about C₂₂ alkyl and R₆ is a

C╬╣-C₆ alkyl and the hydroxy-substituted derivatives thereof; n is an integer

of from about 1 to 4 inclusive with x being a number between 1 and 20,

inclusive, and X can independently be alkyl of 1 to 10 carbon atoms and the hydroxy-substituted derivatives thereof or alkylaryl; and Y independently represents an anion.

2. The biocidal agent of Claim 1 , wherein R is alkyl of from about 6 to about 18 carbon atoms.

3. The biocidal agent of Claim 2, wherein R₂ represents lower alkylene of from 2 to about 6 carbon atoms and the hydroxy substituted derivatives thereof.

4. The biocidal agent of Claim 3, wherein R₂ represents ethylene.

5. The biocidal agent of Claim 4, wherein the Y anion is selected from the group consisting essentially of a halogen, alkylsulfate, phosphate or alkylphosphate.

6. The biocidal agent of Claim 5, wherein the Y anion is chloride.

7. The biocidal agent of Claim 6, wherein the Y anion is methylsulfate or ethylsulfate.

8. The biocidal agent of claim 7, further comprising a surfactant selected from

the group consisting essentially of an anionic, nonionic, cationic, and amphoteric surfactant and mixtures thereof.

. The biocidal agent of claim 8, wherein said nonionic surfactant is selected

from the group consisting of fatty acid glycerine esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyglycerine fatty acid esters, higher alcohol ethylene oxide adducts, single long chain polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene lanolin alcohol,

polyoxyethylene fatty acid esters, polyoxyethylene glycerine fatty acid esters, polyoxyethylene propylene glycol fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene castor oil or hardened castor oil derivatives, polyoxyethylene lanolin derivatives, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amines, alkylpyrrolidones, glucamides, alkylpolyglucosides, mono- and dialkanol amides, polyoxyethylene alcohol mono- or diamides, alkylamine oxides and mixtures thereof.

10. The biocidal agent of claim 8 wherein said anionic surfactant is selected

from the group consisting of fatty acid soaps, ether carboxylic acids and

the salts thereof, alkane sulfonate salts, ╬▒-olefin sulfonate salts, sulfonate

salts of higher fatty acid esters, higher alcohol sulfate ester salts, fatty

alcohol ether sulfate salts, higher alcohol phosphate ester salts, fatty alcohol ether phosphate ester salts, condensates of higher fatty acids and

amino acids, and collagen hydrolysate derivatives.

11. The biocidal agent of claim 8, wherein said cationic surfactant is selected

from the group consisting of alkyltrimethylammonium salts, dialkyl- dimethylammonium salts, alkyldimethylbenzylammonium salts, an alkylpyridinium salt, alkylisoquinolinium salts, benzethonium chloride, acylamino acid type cationic surfactants and mixtures thereof.

12. The biocidal agent of claim 8, wherein said amphoteric surfactant is selected from the group consisting of an amino acids, betaines, sultanes, phosphobetaines, imidazoline-type amphoteric surfactants, soybean phospholipids, yolk lecithins and mixtures thereof.

13. The biocidal agent of claim 12 wherein said imidazoline-type amphoteric

surfactant is selected from the group consisting essentially of cocoamphoacetate and cocodiamphoacetate.

14. The biocidal agent of claim 13, further comprising an auxiliary additive.

15. The biocidal agent of claim 14, wherein said auxiliary additive is selected

from the group consisting of inorganic salts, builders, humectants,

solubilizing agents, UV absorbers, softeners, chelating agents, viscosity modifiers and mixtures thereof.

16. The biocidal agent of claim 15, wherein said surfactant of formula (I) is:

wherein Ri, X and Y are as defined hereinbefore.