Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS3256200 A
Publication typeGrant
Publication dateJun 14, 1966
Filing dateOct 11, 1963
Priority dateMar 9, 1961
Also published asDE1158216B, US3134711
Publication numberUS 3256200 A, US 3256200A, US-A-3256200, US3256200 A, US3256200A
InventorsWilliam C Jordan, Herbert H Reller
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Anti-bacterial detergent composition
US 3256200 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,256,200 ANTI-BACTERIAL DETERGENT COMPOSITION Herbert H. Reller and William C. Jordan, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Original application Mar. 9, 1961, Ser. No. 94,437, now Patent No. 3,134,711, dated May 26, 1964. Divided and this application Oct. 11, 1963, Ser.

1 Claim. (Cl. 252-106) This application is a division of application No. 94,437 filed March 9, 1961, now-Patent No. 3,134,711 issued on May 26, 1964.

This invention relates to improved anti-bacterial agents. More particularly, it relates to anti-bacterial agents which comprise in combination a halogenated salicylanilide and a halogenated trifluoromethyldiphenyl urea compound.

The application of halogenated salicylanilide and trifluoromethyldiphenyl urea compounds as anti-bacterial agents individually has been disclosed in the art. The brorninated salicylanilides have been employed as antibacterial agents in detergent compositions such as deodorant toilet bars, and laundering detergent products.

Anti-bacterial agents which have heretofore been employed in detergent compositions including the said halogenated salicylanilides display certain inherent deficiencies which detract from their efficacy in such applications.

Gram-negative organisms are common contaminates of the skin and other surfaces upon which anti-bacterial detergent usage has been found desirable and it is therefore essential to reduce the population of these organisms as well as gram-positive organisms to obtain the maximum beneficial effect. In general, anti-bacterial agents which have been found satisfactory for use in detergent milieu otherwise, display only slight activity against gram-negative organisms. Both the halogenated salicylanilide and halogenated trifiuoromethyldiphenyl urea compounds are subject to this deficiency, neither compound displaying significant activity against gram-negative organisms at feasible use concentrations.

A disadvantageous characteristic of the widely used bisphenolic compounds is photo-sensitivity. When his- (3,5,6-trichloro-2-hydroxyphenyl) methane and bis(3,4- dichloro-2-hydroxyphenyl) sulfide for example, are incorporated in a toilet detergent bar in concentrations as low as 0.5%, exposure to ordinary daylight results in an unsightly discoloration of the bar. To attain a minimum acceptable level of deodorant effectiveness using the hisphenols in such a bar, at least 2% by weight has been recommended. The degree of discoloration of detergent bars containing this level of bisphenolic compounds is sufficiently great that gold or yellow coloring material must be incorporated in the formulation for masking purposes.

Other anti-bacterial agents, though effective in aqueous solutions are incompatible with detergent actives or at pH values generally characteristic of detergent systems. Thus, the anti-bacterial activity of phenols for example, is almost completely lost in soap milieu. Quaternary ammonium compounds are similarly incompatible with soap and anionic synthetic detergents. I

It is an object of this invention to provide a composition having a high level of anti-bacterial activity.

It is a further object of this invention to provide an anti-bacterial composition which is effective against both gram-positive and gram-negative bacteria.

It is a still further object of this invention to provide an anti-bacterial composition which is adapted to use in detergent milieu.

Other objects and improvements will become apparent from the following description.


X1 OH O Y X2 X1 Y wherein each X represents hydrogen or halogen, X represents a halogen, and Y represents hydrogen, halogen or trifiuoromethyl.

The preferred halogenated salicylanilides which are encompassed by the above general formula include 3,5,4'-tribromosalicylanilide, 5-bromosalicyl-3,5-di(trifluoromethyl)anilide, 5 chlorosalicyl 3,5-di(trifluoromethy1)anilide, 3,S-dichlorosalicyl-3,4-dichloroanilide and 5- chlorosalicyl 3 -trifluoromethyl-4-chloroanilide. Other halogenated salicylanilides which come within the above general formula and display synergistic activity in conjunction with the urea derivatives of this invention are disclosed by Bindler and Model in U.S. Patent 2,703,332, granted March 1, 1955. This patent further discloses a method for their preparation.

The trifiuoromethyldiphenyl urea compounds which can be used in this invention are represented by the general structural formula:

wherein Z represents hydrogen, halogen or trifluoromethyl, X represents halogen or ethoxy, X represents hydrogen or halogen and Y represents hydrogen or trifiuoromethyl. The preferred compounds of this group include 3-trifiuoromethyl 4,4 dichlorocarbanilide, 3 trifluoromethyl- 3',4,4' trichlorocarbanilide, 3,3 bis(trifluoromethyl)-4- ethoxy-4.-chlorocarbanilide, and 3,5-bis(trifluoromethyl)- 4-chlorocarbanilide. These and other operable halogenated trifluoromethyldiphenyl urea compounds are more fully described in U.S. Letters Patent 2,745,874, granted May 15, 1956.

The anti-bacterial efficacy of the synergistic combinationsof this invention was established by determining their bactericidal activity in accordance with the methods developed by Cade and Halverson. (Oade, A. R., and Halverson, H. 0., Soap, vol. 10, #9, page 25.) Antibacterial activity is expressed herein in terms of the percent re-duction in number of viable microorganisms following exposure of a suspension of either Staphylococcus aure'us as the representative gram-positive organism or Escherichia coli as the representative gram-negative or- Concentration/micrograms Percent Reduction Example Total 3-trifluoro- 3,5,4-trimethyl-4,4- bromo sali- E. coli S. dichlorocarcylanilidc aurws banilide The activity of the mixtures of the above examples was determined in accordance with the method referred to above, i.e., suflicient anti-bacterial agent was added to a tube of FDA nutrient broth (US. Dept, of Agriculture Circular 198,-December 1931, page 4) to attain the desired concentration. The suspending fluid and anti-bacterial agent were heated to 37 C. and inoculated with approximately five million cells of the test organisms. These mixtures were then incubated for 10 minutes and an aliquot was removed, diluted in 0.1% peptone water diluent, and placed on B.=B.L. trypticase soy agar (supplied by Baltimore Biological Laboratories, Baltimore, Maryland). After solidification of the agar, the petri dishes were incubated for 24 hours and the number of colonies arising in that time was determined. The number of cells surviving exposure to the anti-bacterial was compared to the number contained in the original inoculum and the figure thus derived was adjusted in consideration of appropriate controls to give the percentage re duction value here employed. It can be seen that neither anti-bacterial agent by itself displays the degree of antibacterial activity attained with the combinations.

The efficacy of the mixture of this invention in soap and non-soap synthetic detergent milieu may be observed from the following examples.

Various concentrations of 3,5,4-tribromosalicylanilide and 3-trifiuoromethyl-4,4-dichloro-carbanilide were added to an aqueous solution containing 250 micrograms/ml. of a neutral white, high grade soap consisting of a mixture of 80% sodium soap and potassium soap derived from a blend of 70% tallow and coconut fatty acids. Total anti-bacterial agent concentration was maintained at 5 micrograms/ml. or 2% by weight of the -soap. The compositions thus prepared were tested for bactericidal activity using the method described supra. The following table presents the results of these tests, each value being an average obtained in several runs.

The percent reduction in numbers of organisms attributable to the respective anti-bacterial agents in soap solution is comparable to the values obtained when the same agents are tested in aqueous milieu.

Similar results are obtained when the other trifluoromethyldiphenyl urea compounds described as operable herein are employed in the soap matrix in place of 3- trilluoromethyl-4,4-dichlorocarbanilide. Substitution of 3,4,4'-tribromosalicylanilide with the otherhalogenated salicylanilides of this invention, such as S-bromosalicyl- 3,5-bis(trifluoromethyl)anilide, 5-chlorosalicyl-3,5-di(tri fluoromethyl) ani-lide, 3,5-dichlorosalicyl-3,4-dichloroanilide and 5-chlorosalicyl-3-trifluoromethyl-4-chlorocarbanilide, results in comparable reductions in numbers of viable organisms. Further, variation of the soap matrix does not have any significant influence on the relative increase in activity attributable to the anti-bacterial agent.

Regular use of a soap bar containing 1% of a 1:1 mixture of halogenated salicylanilide and halogenated trifiuoromethyldiphenyl urea of this invention results in substantial reduction in the bacterial population of the skin and thus markedly reduces body odor attributable to bacterial degradation of perspiration.

The mixtures of this invention have been found to significantly increase the anti-bacterial activity of nonsoap synthetic detergent compositions including both anionic and nonionic and solid or liquid'types. Although some of the detergents in the anionic group, for example, alkyl benzene sulfonate, have substantial anti-bacterial effect against gram-positive microorganisms, few have significant effect against gram-negative organisms. The incorporation of a small amount of halogenated salicylanilide-halogenated trifiuoromethyldiphenyl urea mixtures of this invention in synthetic detergent compositions will effect an increase in anti-bacterial activity against grampositive organisms and will impart significant levels of anti-bacterial activity against gram-negative organisms.

The anionic synthetic detergent which can be employed with this invention is generally defined as a water-soluble salt of an organic sulfuric reaction product having in its molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the synthetics of this group which may be benefited through the incorporation therein of the mixtures of this invention, are the sodium or potassium alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, especially those of the types described in U.S. Letters Patent 2,220,099, granted November 5, 1940, and 2,477,383, granted July 26, 1949, in which 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 obtained from tallow and cononut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates, sodium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or cononut oil alcohols) and about three moles of ethylene oxide, and others known in the art, a number being specifically set forth in Byerly, U.S. Letters Patent 2,486,921, granted November 1, 1949, and Strain, U.S. Letters Patent 2,486,922, granted November 1, 1949.

The nonionic synthetic detergents hereinbefore described as beneficially aifected by the antibacterial mixtures of this invention may be broadly defined as compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.

For example, a well-known class of nonionics to which significant levels of anti-bacterial activity will be imparted through the incorporation of minor amounts of halogenated salicylanilide-trifluoromethylcarbanilide mixture is marketed under the trade name Pluronic by the Wyandotte Chemical Co. of Wyandotte, Michigan. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of pro pylene oxide with propylene glycol.

Other nonionics which are suitable for use with the mixtures of this invention include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having a straight or branched chain alkyl group containing from about 6 to 12 carbon atoms, with from about to about 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in each compound can be conveniently derived from polymerized propylene diisobutylene, octane, or nonane or from any other natural or artificial source which will provide alkyl chains with the requisite number of carbon atoms as specified hereinfore.

Other suitable nonionics may be derived by the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.

A minor amount of a 1:1 mixture of 3,5,4-tribromosalicylanilide and 3-tri=fluoromethyl-4,4-dichlorocarbanilide, for example, renders a composition containing any of the above detergents or mixtures thereof, anti-bacterially active against a broad range of microorganisms including some which are gram-negative.

Detergent compositions containing the anti-bacterial mixtures of this invention find utility in a variety of applications and physical forms as will be recognized by those skilled in the art. Such products may be used as toilet detergent bars, for example, the anti-bacterial mixture being present in amounts varying from 0.1% to 10% by weight of the total composition. Preferably, the bar would contain the said anti-bacterial mixtures in amount varying from .5 to 2% by weight of the total composition.

Example X A milled toilet detergent bar was prepared in accordance with methods known and used in the art and having the following composition.

Percent Sodium alkyl glyceryl ether sulfonate (alkyl group derived from the middle-cut of alcohols obtained by catalytic reduction of coconut oil) 8.0 Potassium alkyl sulfate (alkyl group derived from the -middle-cut* of alcohols obtained by catalytic reduction of coconut oil) 20.0 Magnesium soap of 80:20 tallow: coconut fatty acids 16.7

Sodium soap of 80:20 tallow: coconut fatty acids 32.4 Inorganic salts (sodium and potassium chlorides and sulfates) 9.2 3-trifiuoromethyl-4,4'-dichlorocarbanilide 1.0 3 ,5 ,4-.tribromosalicylanilide 1.0

Water and miscellaneous 11.7

6 romethyl) 4-ethoxy-4 chlorocarbanilide or 3,5-bis('trifluoromethyl)-4-chlorocarbanilide in place of 3-trifluoromethyl-4,'4'-dichlorocarbanilide. Similarly, 3,5,4-.tribromosalicylanilide can be replaced by any of the other halogenated salicylanilides of this invention, such as 5- bromosalicyl-3,5-di(trifluoromethyl) anilide, S-chlorosalicy'l-3,5-di(tri fluorornethyl) anilide, 3,5-dichlorosa-licyl- 3,4-di-chloroanilide or 5-chlorosalicyl-3-trifluoromethyl- 4-chloranilide without decreasing the deodorant eflicacy of the product.

Example XI A granular built synthetic anionic laundry detergent composition having the following formulation was prepared by conventional means.

Parts Sodium alkyl benzene sulfonate (the alkyl radical averaging about 12 carbon atoms and being derived from polypropylene) 17.5 Sodium t-ripolyphosphate 49.7 Sodium sulfate 13.3 Silicate solids 7.0 3-trifluoromet-hyl-3,4,4-trichlorocarbanilide .05 3,5,4-tribromosalicylanilide .05

Fabrics laundered in this product were imparted with substantial levels of anti-bacterial activity as was demonstrated by a marked reduction in surviving organisms when a suspension of viable test organisms were exposed to the laundered material.

The invention has been described above in conjunction with various illustrative examples of anti-bacterial compositions, toilet and laundry detergents. It will be obvious to those skilled in the art, however, that the anti-bacterial mixtures can also be beneficially employed in such products as tooth powder, toothpaste, mouth-wash antiseptic ointment, foot powders and the like.

What is claimed is:

An anti-bacterial detergent composition consisting essentially of a surface active compound selected from the group consisting of anionic and nonionic organic detergents, and from about 0.1% to about 10% of a synergistic combination of 3,5,4'-tribromosalicylanilide and 3- trifluor-omethyl-4,4'-dichlorocarbanilide in a ratio from 1:9 to 9: 1.

References Cited by the Examiner UNITED STATES PATENTS 2,703,332 3/1955 Bindler et al 260-559 2,745,874 5/1956 Schetty et al. 2160-553 3,041,236 6/1962 Stecker 252-l06 XR 3,057,920 lO/l962 Schramm 252-l06 XR JULIUS GREENWALD, Primary Examiner.


Assistant Examiners.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2703332 *Dec 23, 1952Mar 1, 1955 Poly halo-salicylanilioes
US2745874 *Jun 16, 1954May 15, 1956Geigy Ag J RInsecticidal derivatives of diphenyl urea
US3041236 *Sep 18, 1959Jun 26, 1962Herbert C SteckerGermicides containing trifluoromethyl halogenated salicylanilides
US3057920 *Dec 5, 1957Oct 9, 1962Lever Brothers LtdProcess for preparing 3, 4', 5-tribromosalicylanilide in acetic acid
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3981814 *Apr 21, 1975Sep 21, 1976Givaudan CorporationBacteriostatic substituted benzanilide compositions and methods for their use
US3989827 *Oct 8, 1971Nov 2, 1976Colgate-Palmolive CompanyAntibacterial composition
US5968539 *Jun 4, 1997Oct 19, 1999Procter & Gamble CompanyMild, rinse-off antimicrobial liquid cleansing compositions which provide residual benefit versus gram negative bacteria
US6183757Jun 4, 1997Feb 6, 2001Procter & Gamble CompanyMild, rinse-off antimicrobial cleansing compositions which provide improved immediate germ reduction during washing
US6183763Jun 4, 1997Feb 6, 2001Procter & Gamble CompanyAntimicrobial wipes which provide improved immediate germ reduction
US6190674Jun 4, 1997Feb 20, 2001Procter & Gamble CompanyLiquid antimicrobial cleansing compositions
US6190675Nov 12, 1997Feb 20, 2001Procter & Gamble CompanyMild, rinse-off antimicrobial liquid cleansing compositions which provide improved residual benefit versus gram positive bacteria
US6197315Jun 4, 1997Mar 6, 2001Procter & Gamble CompanyAntimicrobial wipes which provide improved residual benefit versus gram negative bacteria
US6210695Jun 4, 1997Apr 3, 2001The Procter & Gamble CompanyLeave-on antimicrobial compositions
US6214363Nov 12, 1997Apr 10, 2001The Procter & Gamble CompanyLiquid antimicrobial cleansing compositions which provide residual benefit versus gram negative bacteria
US6284259Nov 12, 1997Sep 4, 2001The Procter & Gamble CompanyAntimicrobial wipes which provide improved residual benefit versus Gram positive bacteria
US6287577Nov 12, 1997Sep 11, 2001The Procter & Gamble CompanyLeave-on antimicrobial compositions which provide improved residual benefit versus gram positive bacteria
US6287583Nov 12, 1997Sep 11, 2001The Procter & Gamble CompanyLow-pH, acid-containing personal care compositions which exhibit reduced sting
US7319112Sep 15, 2003Jan 15, 2008The Procter & Gamble Co.Non-halogenated antibacterial agents and processes for making same
US20040072908 *Sep 15, 2003Apr 15, 2004The Procter & Gamble Co.Non-halogenated antibacterial agents and processes for making same
EP0496433A2Oct 18, 1988Jul 29, 1992THE PROCTER & GAMBLE COMPANYPhotoprotection compositions comprising chelating agents
EP0496434A2Oct 18, 1988Jul 29, 1992THE PROCTER & GAMBLE COMPANYPhotoprotection compositions comprising chelating agents
WO2002005643A2 *Jul 15, 2001Jan 24, 2002Procter & GambleBiocide compositions and methods and systems employing same
U.S. Classification510/388, 510/319, 510/491, 510/501, 510/502, 514/162, 510/133
International ClassificationC11D3/48, A01N47/30
Cooperative ClassificationA01N47/30, C11D3/48, A61K31/60, A61K31/621
European ClassificationC11D3/48, A01N47/30, A61K31/60, A61K31/621