US3256200A - Anti-bacterial detergent composition - Google Patents

Anti-bacterial detergent composition Download PDF

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US3256200A
US3256200A US320598A US32059863A US3256200A US 3256200 A US3256200 A US 3256200A US 320598 A US320598 A US 320598A US 32059863 A US32059863 A US 32059863A US 3256200 A US3256200 A US 3256200A
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bacterial
detergent
soap
alkyl
activity
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US320598A
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Herbert H Reller
William C Jordan
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to NL120998D priority Critical patent/NL120998C/xx
Priority to NL275155D priority patent/NL275155A/xx
Priority to US94437A priority patent/US3134711A/en
Priority to DEP28856A priority patent/DE1158216B/en
Priority to GB9251/62A priority patent/GB994705A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to US320598A priority patent/US3256200A/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/60—Salicylic acid; Derivatives thereof
    • A61K31/618—Salicylic acid; Derivatives thereof having the carboxyl group in position 1 esterified, e.g. salsalate
    • A61K31/621—Salicylic acid; Derivatives thereof having the carboxyl group in position 1 esterified, e.g. salsalate having the hydroxy group in position 2 esterified, e.g. benorylate
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/60—Salicylic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Z represents hydrogen, halogen or trifluoromethyl
  • X represents halogen or ethoxy
  • X represents hydrogen or halogen
  • 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.
  • 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 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.

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Description

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.
"ice
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.
ALBERT T. MEYERS, w. E. SCHULZ,
Assistant Examiners.
US320598A 1961-03-09 1963-10-11 Anti-bacterial detergent composition Expired - Lifetime US3256200A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL120998D NL120998C (en) 1961-03-09
NL275155D NL275155A (en) 1961-03-09
US94437A US3134711A (en) 1961-03-09 1961-03-09 Halogenated salicylanilide-halogenated trifluoromethyldiphenyl urea synergistic composition
DEP28856A DE1158216B (en) 1961-03-09 1962-02-26 Bactericidal agent
GB9251/62A GB994705A (en) 1961-03-09 1962-03-09 Anti-bacterial compositions
US320598A US3256200A (en) 1961-03-09 1963-10-11 Anti-bacterial detergent composition

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US94437A US3134711A (en) 1961-03-09 1961-03-09 Halogenated salicylanilide-halogenated trifluoromethyldiphenyl urea synergistic composition
US320598A US3256200A (en) 1961-03-09 1963-10-11 Anti-bacterial detergent composition

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US94437A Expired - Lifetime US3134711A (en) 1961-03-09 1961-03-09 Halogenated salicylanilide-halogenated trifluoromethyldiphenyl urea synergistic composition
US320598A Expired - Lifetime US3256200A (en) 1961-03-09 1963-10-11 Anti-bacterial detergent composition

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US94437A Expired - Lifetime US3134711A (en) 1961-03-09 1961-03-09 Halogenated salicylanilide-halogenated trifluoromethyldiphenyl urea synergistic composition

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US3981814A (en) * 1973-09-18 1976-09-21 Givaudan Corporation Bacteriostatic substituted benzanilide compositions and methods for their use
US3989827A (en) * 1965-10-22 1976-11-02 Colgate-Palmolive Company Antibacterial composition
GB2243615A (en) * 1990-05-04 1991-11-06 Procter & Gamble Beta-phase soap bars containing solubilized solid antibacterial agent
EP0496434A2 (en) 1987-10-22 1992-07-29 The Procter & Gamble Company Photoprotection compositions comprising chelating agents
US5968539A (en) * 1997-06-04 1999-10-19 Procter & Gamble Company Mild, rinse-off antimicrobial liquid cleansing compositions which provide residual benefit versus gram negative bacteria
US6183757B1 (en) 1997-06-04 2001-02-06 Procter & Gamble Company Mild, rinse-off antimicrobial cleansing compositions which provide improved immediate germ reduction during washing
US6183763B1 (en) 1997-06-04 2001-02-06 Procter & Gamble Company Antimicrobial wipes which provide improved immediate germ reduction
US6190674B1 (en) 1997-06-04 2001-02-20 Procter & Gamble Company Liquid antimicrobial cleansing compositions
US6190675B1 (en) 1997-06-04 2001-02-20 Procter & Gamble Company Mild, rinse-off antimicrobial liquid cleansing compositions which provide improved residual benefit versus gram positive bacteria
US6197315B1 (en) 1997-06-04 2001-03-06 Procter & Gamble Company Antimicrobial wipes which provide improved residual benefit versus gram negative bacteria
US6210695B1 (en) 1997-06-04 2001-04-03 The Procter & Gamble Company Leave-on antimicrobial compositions
US6214363B1 (en) 1997-11-12 2001-04-10 The Procter & Gamble Company Liquid antimicrobial cleansing compositions which provide residual benefit versus gram negative bacteria
US6284259B1 (en) 1997-11-12 2001-09-04 The Procter & Gamble Company Antimicrobial wipes which provide improved residual benefit versus Gram positive bacteria
US6287583B1 (en) 1997-11-12 2001-09-11 The Procter & Gamble Company Low-pH, acid-containing personal care compositions which exhibit reduced sting
US6287577B1 (en) 1997-11-12 2001-09-11 The Procter & Gamble Company Leave-on antimicrobial compositions which provide improved residual benefit versus gram positive bacteria
WO2002005643A3 (en) * 2000-07-14 2003-07-17 Procter & Gamble Biocide compositions and methods and systems employing same
US20040072908A1 (en) * 2000-07-14 2004-04-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same

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US3303136A (en) * 1963-02-26 1967-02-07 Lever Brothers Ltd Detergent compositions
US3244585A (en) * 1964-01-29 1966-04-05 Herbert C Stecker Stabilized halosalicylanilide germicides
US4118332A (en) * 1965-10-22 1978-10-03 Colgate-Palmolive Company Synergistic antibacterial composition containing mixtures of certain halogenated diphenyl ethers and trichlorocarbanilides

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US3041236A (en) * 1959-09-18 1962-06-26 Herbert C Stecker Germicides containing trifluoromethyl halogenated salicylanilides
US3057920A (en) * 1957-12-05 1962-10-09 Lever Brothers Ltd Process for preparing 3, 4', 5-tribromosalicylanilide in acetic acid

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US2745874A (en) * 1953-06-18 1956-05-15 Geigy Ag J R Insecticidal derivatives of diphenyl urea
US3057920A (en) * 1957-12-05 1962-10-09 Lever Brothers Ltd Process for preparing 3, 4', 5-tribromosalicylanilide in acetic acid
US3041236A (en) * 1959-09-18 1962-06-26 Herbert C Stecker Germicides containing trifluoromethyl halogenated salicylanilides

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989827A (en) * 1965-10-22 1976-11-02 Colgate-Palmolive Company Antibacterial composition
US3981814A (en) * 1973-09-18 1976-09-21 Givaudan Corporation Bacteriostatic substituted benzanilide compositions and methods for their use
EP0496434A2 (en) 1987-10-22 1992-07-29 The Procter & Gamble Company Photoprotection compositions comprising chelating agents
EP0496433A2 (en) 1987-10-22 1992-07-29 The Procter & Gamble Company Photoprotection compositions comprising chelating agents
GB2243615A (en) * 1990-05-04 1991-11-06 Procter & Gamble Beta-phase soap bars containing solubilized solid antibacterial agent
GB2243615B (en) * 1990-05-04 1993-03-31 Procter & Gamble Beta-phase soap bars including those containing low level of moisture and solubilized solid antibacterial agent
US6190675B1 (en) 1997-06-04 2001-02-20 Procter & Gamble Company Mild, rinse-off antimicrobial liquid cleansing compositions which provide improved residual benefit versus gram positive bacteria
US6183757B1 (en) 1997-06-04 2001-02-06 Procter & Gamble Company Mild, rinse-off antimicrobial cleansing compositions which provide improved immediate germ reduction during washing
US6183763B1 (en) 1997-06-04 2001-02-06 Procter & Gamble Company Antimicrobial wipes which provide improved immediate germ reduction
US6190674B1 (en) 1997-06-04 2001-02-20 Procter & Gamble Company Liquid antimicrobial cleansing compositions
US5968539A (en) * 1997-06-04 1999-10-19 Procter & Gamble Company Mild, rinse-off antimicrobial liquid cleansing compositions which provide residual benefit versus gram negative bacteria
US6197315B1 (en) 1997-06-04 2001-03-06 Procter & Gamble Company Antimicrobial wipes which provide improved residual benefit versus gram negative bacteria
US6210695B1 (en) 1997-06-04 2001-04-03 The Procter & Gamble Company Leave-on antimicrobial compositions
US6214363B1 (en) 1997-11-12 2001-04-10 The Procter & Gamble Company Liquid antimicrobial cleansing compositions which provide residual benefit versus gram negative bacteria
US6284259B1 (en) 1997-11-12 2001-09-04 The Procter & Gamble Company Antimicrobial wipes which provide improved residual benefit versus Gram positive bacteria
US6287583B1 (en) 1997-11-12 2001-09-11 The Procter & Gamble Company Low-pH, acid-containing personal care compositions which exhibit reduced sting
US6287577B1 (en) 1997-11-12 2001-09-11 The Procter & Gamble Company Leave-on antimicrobial compositions which provide improved residual benefit versus gram positive bacteria
WO2002005643A3 (en) * 2000-07-14 2003-07-17 Procter & Gamble Biocide compositions and methods and systems employing same
JP2004503568A (en) * 2000-07-14 2004-02-05 ザ、プロクター、エンド、ギャンブル、カンパニー Biocide compositions and methods and systems for using biocide compositions
US20040072908A1 (en) * 2000-07-14 2004-04-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same
US7319112B2 (en) 2000-07-14 2008-01-15 The Procter & Gamble Co. Non-halogenated antibacterial agents and processes for making same

Also Published As

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NL120998C (en)
NL275155A (en)
GB994705A (en) 1965-06-10
US3134711A (en) 1964-05-26
DE1158216B (en) 1963-11-28

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