US3560390A - Antimicrobic detergents - Google Patents

Abstract

A MICROBIOCIDAL DETERGENT COMPOSITION COMPRISING A MIXTURE OF (1) A QUATERNARY AMMONIUM COMPOUND AND (2) A SOAP OR NON-SOAP ANIONIC DETERGENT, THE QUATERNARY AMMONIUM COMPOUND BEING PRESENT IN A PROPORTION OF ABOUT 0.1% TO 5.0% BY WEIGHT OF THE COMPOSITION AND CONSISTING OF (A) THE CATIONIC RESIDUE OF A QUATERNARY AMMONIUM COMPOUND HAVING AN ALKYL GROUP OF 12 TO 18 CARBON ATOMS ATTACHED TO THE QUATERNARY NITROGEN AND A PHENOL COEFFICIENT OF AT LEAST 200 AGAINST STAPHYLOCOCCUS AUREUS AND SALMONELLA TYPHOSA AT 20*C., AND (B) AN ORGANIC ANION CONSISTING OF THE RESIDUE OF EITHER AN ACIDIC OR PSEUDOACIDIC ORGANIC COMPOUND HAVING A REPLACEABLE HYDROGEN.

Description

United States Patent 3,560,390 ANTIMICROBIC DETERGENTS Irving Gaines, Montclair, N.J., assignor to Millmaster Onyx Corporation, New York, N.Y., a corporation of New York No Drawing. Continuation-impart of application Ser. No. 602,550, Dec. 19, 1966. This application May 24, 1968, Ser. No. 731,702

Int. Cl. Clld 9/50 US. Cl. 252-107 4 Claims ABSTRACT OF THE DISCLOSURE A microbiocidal detergent composition comprising a mixture of (l) a quaternary ammonium compound and (2) a soap or non-soap anionic detergent, the quaternary ammonium compound being present in a proportion of about 0.1% to 5.0% by weight of the composition and consisting of (a) the cationic residue of a quaternary ammonium compound having an alkyl group of 12 to 18 carbon atoms attached to the quaternary nitrogen and a phenol coetficient of at least 200 against Staphylococcus aureus and Salmonella typlzosa at C., and (b) an organic anion consisting of the residue of either an acidic or pseudoacidic organic compound having a replaceable hydrogen.

This is a continuation-in-part of copending application Ser. No. 602,550, filed Dec. 19, 1966 now abandoned.

This invention relates to a method and means for imparting microbiocidal properties to soap and anionic detergents in either bar, cake, liquid, pellet or bead form.

In accordance with the present invention, certain substantially water-insoluble mutually precipitated cationicanionic-salts having microbiocidal properties are added in suitable proportions, preferably, from about 0.1% to 5.0% by weight, to the soap or detergent. Preferably, the cationic moiety is derived from quaternary ammonium compounds having a phenol coefiicient of at least 200 against both Staphylococcus aureus and Salmonella typhosa at 20 C., when tested by the standard method of the Official Methods of the Association of Official Agricultural Chemists, 9th edition, 1960.

The term soap includes all soaps, both of the alkali metal type and the amine type, all of which, to applicants knowledge, are operative for the present purposes. The term anionic detergent includes all compounds that are embraced by this term, all of which, to applicants knowledge, are operative for the present purposes.

The present compounds, although substantially waterinsoluble, are prepared from water soluble quaternary ammonium germicides that are, in general, commercially available. As indicated previously, it is preferred to employ a class of these germicides which possesses a phenol coefiicient of at least 200 at 20 C., against Staphylococcus aureus and Salmonella typhosa. It is most preferable that those compounds are used which have exceptionally high phenol coefficients; namely, quaternary ammonium compounds possessing one long alkyl radical containing from 12 to 18 carbon atoms but, preferably, either with only C to C groups, or with only a minimum of C groups present, and one benzene nucleus, and having the following general structure:

wherein X is a halogen atom such as chlorine or bromine; R is an alkyl radical having from 12 to 16 carbon atoms;

R may be a benzyl or substituted benzyl radical in which case R and R are methyl radicals; or wherein R, R" and R' together with N constitute the nucleus of a bycyclic heterocycle of aromatic nature.

Where R is a benzyl radical, it may be substituted with one or more halogens such as chlorine, or with one or more alkyl radicals totalling from 1 to 5 carbon atoms such, for example, as ethyl benzyl, dimethyl benzyl, isopropyl benzyl, tertiary butyl benzyl, isoamyl benzyl, tetramethyl benzyl, menaphthyl or tetrahydromenaphthyl radicals.

The quaternary compounds used herein should be substantially Water-insoluble because in that way, reaction with the soap or detergent is avoided and this avoids neutralization of the desirable characteristics of these components. At the same time, even though the quaternary is water-soluble, it is still microbiocidal. Furthermore, it is generally substantive to the surface being treated. In this way, the composition is always both germicidal and sanitizing.

Typical but non-limitative examples of such quaternary ammonium salts, and their phenol coefficients are:

50% C12, 30% C14, 17% Cm, 3% C 0% C14, 30% C14, 5% C12, 5% C1 NOTE.-S.a.=Staphylococcus aurcus; S.t.=SalmoneZla typhosa.

The terms a and b relating to alkyl are used hereinafter to designate the same groupings.

Among the anionic substances which may be used in preparing the cationic-anionic complexes are a wide variety of aliphatic, alicyclic and aromatic carboxylic or sulfonic acids, esters of sulfuric, phosphoric and phosphinic acids, and the like, phenols, nitro compounds, imides, enolates, and many others. However, where the anion is an acid or ester that includes an inorganic radical, such as sulfates, sulfonates, phosphates, etc., it is preferable that the organic radical contain at least 4 carbon atoms if it is aliphatic, and at least 10 carbon atoms, either in the ring structure or in the ring and its side groups, if it is aromatic.

The preparation of the desired cationic-anionic compounds containing the aforesaid anions is, preferably, by metathesis between the alkali-metal or other salts of the anions and the quaternary ammonium salts, in solution in water or other mutual solvent, from which the product may be separated. Alternatively, a quaternary ammonium hydroxide may be prepared and then reacted stoichiometrically with the anion-contributing acidic substance. Either of these types of preparations may be used for any or all the cationic-anionic compounds disclosed herein.

The anionic portion of the cationic-anionic salt may be any non-detergent organic anion that has a replaceable hydrogen, either acidic or pseudoacidic. Exemplifying these anionic moieties are those derived from such acids, esters, or ethers as pentaand tetrachlorophenate, p-

carboalkoxy phenates, salicylaldehyde, branched-chain aliphatic acids such as neo-tridecanoate and the products produced under the name Versatate," metanilate, sulfanilate, phthalate, trimellitate, sulfophthalate, p-toluatc, decyn-4, 7-diolate, 4-ethyl-1-octyne-3-olate, thiodiglycolate, laurylmercaptide, carboxymethyl mercaptosuccinate, chlorendate, camphorate, hexahydrophthalate, salts of acinitrostyrene and acinitrododecane, p-nitrophenyl acetate, benzoates such as halo-benzoates, 3-nitro-4 chlorobenzoate, octylbenzoate and p-amino-benzoate, aminophenylacetate, 4,4-bis(p-hydroxy phenyl) pentanoate and its polyethers, succinimide, adipimide, saccharinate, cyclamate, p-aminophenyl mercaptoacetate, salts of polymeric ethylene maleates, cellulose sulfates, salts of chrysanthemum acids such as 2,2 dimethyl-3-(2-methylpropenyl)cyclopropane carboxylic acid, alphaoctynoate, salts of Z-pyridine thiol-l-oxide, dodecenyl succinate, hexenylsuccinate, chaulmoograte, o-chloromercuriphenate, ochloromercuri p-toluene sulfonate, borohydride, isocinchomeronate, 3-pyridyl sulfonate, 9,10-dibromostearate,

gluconate, ascorbate, salicylanilide, oleylhydroxamate, p-hydroxybenzhydroxamate, 5,5 diethylbarbiturate, cyanurate, ethyl dithiocarbonate, dodecyl dithiocarbonate, p-toluene sulfonamide, dodecylbenzene sulfonamide, di and polycarboxylic aromatic acids, lower alkyl (i.e. isopropyl) naphthalene sulfonate and naphthol sulfonates, suranim, taurocholate, naphthenate, carboxymethyl cellulose, polysaccharide carboxylate, alginate, pectinate, redwood acids, lignin sulfonic acids, alkali lignin, polyacrylates, polymethacrylates, styrenemaleic polymer, vinyl acetate-maleic polymer, polyvinyl and polystyrene sulfonates, mercapto arylene thiazole, l-benzo thiazyl sulfide, dithiocarbamate, benzoic, salicylic, tartaric and citric acids, thiocarbonate, fluoborate, and phthalimide.

The anionic detergents which are compatible with the present cationic-anionic complexes include higher alkyl (dodecyl, tridecyl, etc.) benzene sulfonates, sodium higher alkyl sulfates, higher alkyl ether sulfates and sulfonates, sulfated esters (such as alpha sulfo methyl myristate), sulfated and sulfonated fatty acid monoglycerides, salts of organic phosphoric esters, the fatty acid derivatives of isethionic acid, taurine and sarcosine, sulfated poly alkoxy phenols and alkyl phenols, and any other anionic detergents such as are listed in variety by trade name and by manufacturer or distributor in McCutcheons wellknown annual Detergents and Emulsifiers (John W. McCutcheon, Inc., Morristown, N.I.).

In addition to anionic detergents, these complexes are also compatible with the related anionic wetting agents,

hydrotropes, dispersing agents and emulsifiers; in fact, I

with anionic surface active agents in general.

As illustrative of these anionic substances, but not limitative thereof, are the following commercial products:

Aerosol 18: disodium-N-octadecyl sulfosuccinate Alipal (in variety): e.g. sodium salt of sulfated alkylphenoxyethoxy poly (ethyleneoxy) ethanol Bio-Det M-lOO: sodium salt of alpha sulfo methyl myristate Gafac LO: sodium salt of complex organic phosphate esters Igepon AP: oleic acid ester of sodium isethionate Igepon T: sodium N-methyl-N oleoyl taurate Maprosyl 30: sodium lauroyl sarcosinate Monad G: coco monoglyceride sulfate Maprofix WA: sodium lauryl sulfate Maprofix ES: sodium lauryl ether sulfate Maprofix TLS: triethanolamine lauryl sulfate Onyxol 336: coconut-acid, diethanolamine condensate,

Merely as illustrative of the type of compounds embodying the present invention, and with the understanding that there are a great many more compounds which similarly embody the present invention, are the following: lauryl dimethyl benzyl ammonium metanilate, lauryl isoquinolinium sulfanilate, myristyl dimethyl benzyl ammonium salicylate, myristyl dimethyl benzyl ammonium ethyl p-hydroxy benzoate, lauryl dimethyl benzyl ammonium pyromellitate, lauryl dimethyl menaphthyl ammonium ethyl hexanoate, lauryl ethylbenzyl dimethyl ammonium succinimide, and myristyl dimethyl benzyl ammonium benzene phosphinate.

The invention is illustrated by, but not restricted to, the following examples:

EXAMPLE I A soda soap was boiled, using a 4 to 1 ratio of highgrade tallow to coconut oil, by a standard commercial process, and finished at low free-alkali and salt content to about 62% strength as fatty acid. 98 parts of this was milled along with 2 parts of alkyl dimethyl benzyl ammonium benzene phosphinate.

The mixture was compressed, extruded and formed into cakes or bars of germicidal soap. A portion of the mixture was flaked, and another portion was flaked and comminuted to make a free-flowing powder of the germicidal soap.

Instead of alkyl dimethyl benzyl ammonium benzene phosphinate, an equal amount of alkyl dimethyl ethylbenzyl ammonium epoxystearate or alkyl dimethyl benzyl oleyl hydroxamate may be employed.

EXAMPLE II A liquid germicidal hand-cleaning soap was prepared according to the basic formula for Medicinal Soft Soap presented on page 646 of the Sixteenth Revision of the Pharmacopeia of the United States of America.

650 grams of the soap paste was dissolved in 200 grams of alcohol plus 20- grams of oil of lavender with agitation until it became homogeneous.

10 grams of alkyl isoquinolinium sulfanilate was dissolved in 90 grams of alcohol. This was added to the soap solution until the tincture was homogeneous. After aging for twenty-four hours, the solution was clarified by filtration, and adjusted to make 100 grams by the addition of alcohol.

This was used as a pre-surgical hand-scrubbing soap, and was tested as such by the Price Technique for Determining Degermation of the Skin as described in Antiseptics, Disinfectants, Fungicides, and Chemical and Physical Sterilization edited by George F. Reddish (Lea and Febiger, 1957), pages 101-102. It was found to be equal to or better than a soap containing 2% of hexachlorophene.

Equally effective as the above was a formulation which differed only in that 10 grams of alkyl isoquinolinium cyclamate was substituted for 10 grams of alkyl isoquinolinium sulfanilate.

EXAMPLE III A germicidal household laundry detergent in liquid form was prepared by dissolving 0.5 part of alkyl dimethyl benzyl ammonium nonylphenate in 8.2 parts of propylene glycol and 2 parts of Onyxol 336 (a lauric acid diethanolamine condensate manufactured by Onyx Chemical Company). This was added to 45 parts of Ultrawet 35KX (an alkyl benzene sodium sulfonate, 31.5% active manufactured by Atlantic Refining Company), along with 0.3 part of carboxymethyl cellulose. When thoroughly and uniformly mixed, 20 parts of tetrapotassium pyrophosphate and 3 parts of sodium metasilicate were added, followed by 21 parts of water, and the mixing was continued until all the components were fully dissolved.

Instead of alkyl dimethyl benzyl ammonium nonylphenate, an equal quantity of alkyl dimethyl benzyl ammonium chlorendate, or of alkyl dimethyl ethylbenzyl ammonium neo-tridecanoate may be substituted.

EXAMPLE IV A heavy-duty liquid household detergent was prepared consisting of the following:

Parts by weight Tetrapotassium pyrophosphate Sodium xylene sulfonate (40%) 5 Superamide GR (coconut fatty acid diethanolamine condensate, 80% active manufactured by Onyx Chemical Company) 5 Ultrawet 60L (alkyl benzene sulfonate, 60% active manufactured by Atlantic Refining Company) 10 Pine oil 1 Water 68.5 Alkyl dimethyl benzyl ammonium tetrachlorophenate 0.3

The quaternary ammonium compound was dissolved in the Superamide GR and the pine oil and added to the Ultrawet and the sodium xylene sulfonate with agitation. The pyrophosphate was dissolved in part of the water and added to the other components along with the rest of the water.

Instead of alkyl dimethyl benzyl ammonium tetra-. chlorophenate, alkyl isoquinolinium 2,4 dichlorobenzoate may be used.

EXAMPLE V A powder detergent was prepared in a tumble mixer. 10 parts of alkyl dimethyl benzyl ammonium Versatate 9-11 was blended into 400 parts of 40% active powdered alkyl-benzene sodium sulfonate and 50 parts of 90% active sodium lauryl sulfate powder until the powders were thoroughly and uniformly coated. Builders consisting of 150 parts of sodium tripolyphosphate, 50 parts of sodium metasilicate and 150 parts of sodium sulfate were added along with 5 parts of carboxymethyl cellulose, and tumbled until the mixture was homogeneous.

This powder is suitable for dishwashing or for home machine laundering.

Alkyl dimethyl dimethyl-benzene ammonium salt of 1-phenyl-l,3-butanedione or alkyl dimethyl ethylbenzyl ammonium p-phenyl phenate may be substituted for the alkyl dimethyl benzyl ammonium Versatate.

EXAMPLE VI A sanitizing rug cleaner or rug shampoo was formulated as follows:

Parts by weight Oleic acid 22.0 Coconut fatty acids 17.0 Triethanolamine 11.0 Monoethanolamine 5.5

Neutronyx 600 (alkyl-phenol polyglycol ether manufactured by Onyx Chemical Company) 4.0 Cetyl pyridinium chaulmoograte 1.0 Isopropanol (99%) 25.0 Water 14.5

The above components were mixed and agitated, at about 50 C., and ambient pressure, until a homogeneous liquid was formed. Instead of cetyl pyridinium chaulmoograte, the corresponding Versatate 1519 may be substituted.

EXAMPLE VII The same procedure was used as in Example I except that instead of 98 parts of the soda soap, only 91 parts were used together with 8 parts of 88% active Gafac LO-529. Furthermore, instead of 2 parts of the alkyl dimethyl benzyl ammonium benzene phosphinate, 1 part of lauryl dimethyl benzyl ammonium pyromelitate was used. The resultant product was an excellent bar soap.

EXAMPLE VIII The same procedure was used as in Example VI but with the following ingredients:

6 RUG SHAMPOO Parts by weight 26 /2 ammonium lauryl sulfate 30% ammonium lauryl sarcossinate 5 Lauryl isoquinolinium sulfanilate 0.3 Water 71 The resultant product was an excellent rug shampoo.

EXAMPLE IX A wool scouring agent was prepared by mixing the following ingredients at room temperature and pressure:

WOOL SCOURING AGENT Parts by weight disodium-N-octadecyl sulfosuccinamate 5 Nonyl-phenol ethylene-oxide adduct (Neutronyx- 600, Onyx Chemical Co.) 2 Myristyl dimethyl benzyl ammonium tri-bromosalicylanilide 0.05 Sodium sulfate 3.0

Water 90 EXAMPLE X A hand dishwashing detergent composition was prepared by mixing the following ingredients at room temperature and pressure, after heating the diethanolamide to about C., to liquify it:

Parts by weight 28% Alipal CO-433 1 30 98% lauric diethanolamide 2 Myristyl dimethyl benzyl ammonium benzyl phosphinate 0.4 Propylene glycol 2 Water 1 Sodium salt of a sulfate ester of alkylphenoxy poly (ethyleneoxy) etl1anol EXAMPLE XI A hard surface floor cleaner was prepared by mixing the following ingredients at room temperature and pressure:

Parts by weight Onyxol 336 8 Gafac LO-529 2 Sodium tripoly phosphate 5 Lauryl ethylbenzyl dimethyl ammonium hexahydrophthalate 0.1 Water 84 EXAMPLE XII A hair shampoo was prepared by mixing the following ingredients at room temperature and pressure, after heating the diethanolamide to about 50 C., to liquify it:

Parts by weight 30% Maprofix ES 30 98% lauric diethanolamide 5 Lauryl dimethyl menaphthyl ammonium ethyl hexanoate 0.4

Water 64 The biological activity of the cationic-anionic compounds of this invention may be evaluated for biological stasis by the Standard Tube Dilution Test, the technique for which is common knowledge to those skilled in the art. A Difco Bacto CSMA Broth #0826 is used in this study. This test is used to determine the lowest concentration of biologically active compounds which will inhibit the growth of the organism in question. For a wide range of applications, the inhibition of growth rather than outright kill is satisfactory.

Briefly put, the Tube Dilution Test consists in putting 9 cc. of the CSMA Broth in a test tube which is then sterilized in an autoclave. One cc. of a solution of the biologically active compound at an appropriate concentration is added to the test tube which is then inoculated with 0.1 cc. of a twenty-four hour old culture of the organism under study. The test tube is then incubated at 37 C., for forty-eight hours and observed for bacterial growth.

The same procedure is followed for fungi. They are, however, incubated for fourteen days at a temperature suitable for optimum growth.

The biostatic dilutions of these new compounds were evaluated against the following organisms:

Staphylococcus aureus (FDA #209) Salmonella typhosa (Hopkins Strain) Aspergillus niger Trichophyton interdigitale Pityrosporum ovale Penicillium luteum Typical examples of the values obtained for static dilution on some of these preparations are as follows:

TABLE 2 Reciprocal of static dilution of product vs.-

Cation Anion S.a. S.t. A11.

Alkyh, dimcthyl Chlorcndate 10 10 10 ethylbenzyl Tetrachlorophenate 10 10f 10 ammonium. {:aurylmercaptidc apoxystearate Alkylbt dunethtll- Sorbic hydroxamate 10 10 10 benzyl ammonium Nmodecane 106 105 104 Phenol phosphinate. 10 10 10 l n i m {l-phenyl-l,3-butanedione 10 10 10 1 Oqu n u Dinitro o-cyclohexylphcncl 10 10 Dcdecyl dimethyl C 1 te 106 105 menaphthyl ye 7 7 6 ammoniunh Sacchaunate 10 10 10 NorE.-S.a.=Staphylococcus aureus, S.t.=Salmonclla typhosa; A.n.= Aspergillus 'm'ger.

Preparations such as those described in the above examples, while non-toxic and non-irritating in use dilutions and not more so in concentrated form than the detergents themselves, nevertheless are effective bacteriostatic and fungistatic agents. Such microorganisms as are not washed away by detergent action or destroyed by germicidal action, are inhibited in growth by residual traces of quaternary ammonium compound.

Fabrics laundered thus commercially, domestically or in hospitals are rendered resistant to the growth of microorganisms. The likelihood of cross infection from linens previously used by other persons, or as the result of intermediate handling, is greatly reduced. Diapers and other infant clothing so laundered tend to reduce the incidence of diaper rash caused by ammonia producing organisms.

Surgical hand soaps so formulated are at least as eifective as compositions containing phenolics, and often appreciably more effective in reducing the bacterial count after scrubbing the hands therewith. Floors, tiles, walls, tables and other surfaces cleaned with my detergent compositions are rendered resistant to the growth of air-borne or trafiic-carried microorganisms. Dishes and glassware may be sanitized as well as cleansed in the process of dishwashing either mechanically or manually.

Similarly, wherever detergency is required, a greater or lesser degree of sanitization can be imparted by the use of formulations such as those described in the above examples, the degree of sanitization depending in general on the amount of quaternary ammonium compound included in the detergent mixture, and also on its specific nature.

The compounds of this invention possess a variety of characteristics which make them superior to currently used germicides in combination with soaps or detergents. The compounds of this invention are readily miscible with soaps and detergents and have no disagreeable odor which must be masked. They have no tendency to bloom on the surface of solid bars nor do they cause statification of liquid formulations.

An outstanding characteristic of the compounds of this invention is their substantivity to a wide. variety of surfaces. This substantivity imparts long lasting bacteriostatic properties to surfaces washed with compositions containing the compounds of this invention, whereas, known germicides have only transient activity when incorporated in washing compositions.

Obviously, many modifications of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

The invention claimed is:

1. A microbiocidal detergent composition consisting essentially of (1) about 0.1% to 5.0% by weight of a substantially water-insoluble quaternary ammonium compound and (2) an effective amount of a detergent selected from the group consisting of soap and non-soap synthetic anionic detergents, the quaternary ammonium compound having the structure:

wherein R is an alkyl group having from 12 to 18 carbon atoms, R is either benzyl or lower alkyl substituted and halogen substituted benzyl, in which case R" and R' are methyl, or R, R" and R, together with N, constitute a heterocyclic nucleus, and wherein X is the anionic residue of a member of the group consisting of neo-tridecanoate, mixtures of branched chain saturated carboxylic acids containing 9 to 11 carbon atoms, hexanoate, decyn-4, 7-diolate, 4-ethyl-1-octyne-3-olate, thiodiglycolate, laurylmercaptide, carboxymethyl mercaptosuccinate, camphorate, acinitrostyrene, nitrodecane, acinitrododecane, succinimide, adipimide, cyclamate, cellulose sulfate, 1 phenyl 1,3-butanedione, alphaoctynoate, 2 pyridine thiol 1 oxide, dodecenyl-succinate, hexenylsuccinate, chaulrnoograte, o-chloromercuri-p-toluene sulfonate, isocinchomeronate, 3-pyridyl sulfonate, 9,10-dibromostearate, gluconate, ascorbate, epoxystearate, sorbic hydroxamate, oleylhydroxamate, p hydroxybenzhydroxamate, 5,5 diethylbarbiturate, cyanurate, ethyldithiocarbonate, dodecyldithiocarbonate, suranim, taurocholate, carboxymethyl cellulose, alginate, pectinate, l-benzothiazyl sulfide, dithio-carbamate, thiocarbonate and fluoborate.

2. The composition of claim 1 as a powder.

3. The composition of claim 1 as a liquid.

4. The composition of claim 1 as a shaped body.

References Cited UNITED STATES PATENTS 2,395,989 3/1946 Bock et al. 260-583 2,541,816 2/1951 Glarum et al 260-567.5 2,725,326 11/1955 Shibe et al. 424-270 2,865,805 12/1958 Frant et al. 260-567.6X 2,961,466 11/1960 Nielsen 260-567.6 3,235,556 2/1966 Wakeman 260-286 3,299,073 l/1967 Wakeman 260-286 3,417,184 12/1968 Wakeman 252-107X 2,541,248 2/1951 Hibbs 424-329 2,861,955 11/1958 Aylesworth 252-117 3,351,652 11/1967 Wakeman et al 260-473 3,393,194 7/1968 Baravalle 260-247.7

OTHER REFERENCES Shibe et al.: Soap and Chem. Specialties, Quaternary Ammonium Compounds. July 1964, pp. 8385, 88, 89.

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252-106; 424-329 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,560,390 Dated February 2 1971 Inventor(s) Irving Gaines It is certified that error appears in the above-identified paten and that said Letters Patent are hereby corrected as shown below:

Column 2, line 17: "water-soluble" is changed to "water-insoluble" Signed and sealed this 7th day of September 1971 (SEAL) Attest:

EDWARD M .FLETCHER, JR. ROBERT GO'ITSCHALK Acting Commissioner of Pat Attesting Officer F OHM PO-1050 (10-69)