US3503886A - Antiseptic compositions - Google Patents

Description

United States Patent US. Cl. 252-107 11 Claims ABSTRACT OF THE DISCLOSURE Soap compositions containing a synergistic germicidal combination of hexachlorophene and certain substituted carbanilides. The ratio of the hexachlorophene to the carbanilide being 1:1.

This application is a streamlined continuation of application Ser. No. 446,143 filed Apr. 5, 1965, now abandoned. This application is also a continuation-in-part of our copending application Ser. No. 184,672 filed Apr. 3, 1962, now US. Patent 3,177,115, and our copending application Ser. No. 394,628 filed Sept. 4, 1964, now abandoned.

This invention relates to antiseptic compositions having synergic effect. In one of its aspects this invention relates to improved germicidal cleansing compositions containing as their essential germicidal ingredients a synergistic combination of either an unalkylated or alkylated polyhalobisphenol and certain substituted carbanilides.

The popularity of germicidal cleansing compositions for laundry and toilet use has increased tremendously over the past few years. In fact, it has been estimated that better than 20% of bar soap sales now are of products containing a germicidal agent, and this percentage is steadily increasing. There are a number of germicidal agents currently in use, but the unalkylated halogenated bisphenols appear to be the most widely accepted because of their activity, compatibility and commercial availability. One of the compounds of this class is 2,2'-dihydroxy-3,5,6,3',5,6-hexachlorodiphenyl methane, commonly known as hexachlorophene, which is now in widespread commercial use. Another example is 2,2-dihydroxy-3,5,3',5'-tetrachlorodiphenyl sulfide, commonly known as bithionol. The action of halogenated bisphenols such as hexachlorophene when incorporated in soap, the proportions required, and other pertinent information, is set out more fully in US. Patent No. 2,535,077 to Kunz et al.

There are certain inherent disadvantages to the use of both unalkylated and alkylated halogenated bisphenols. For example, they are photo-sensitive and tend to cause discoloration in the finished product upon exposure to light. Hence, they cannot be used in a pure white soap. Also, they are somewhat toxic and present a potential hazard to domestic animals which are prone to eat things, even soap. Therefore, it would be desirable to diminish these disadvantages without adversely affecting their germicidal activity. From a different point of view, it would also be worthwhile if these disadvantages could be maintained at their present level and the germicidal activity of the unalkylated and alkylated halogenated bisphenols increased. We have discovered that these objects can be accomplished through the production of a synergic effect.

In accordance with the present invention, the germicidal activity of unalkylated and alkylated halogenated bisphenols in antiseptic compositions is enhanced, synergized or potentiated by the incorporation therewith of a substituted carbanilide. The products of the invention, therefore, are antiseptic compositions containing as their essential active ingredients a synergistic combination of either an unalkylated or alkylated halogenated bisphenol and a substituted carbanilide.

For the purposes of this invention, any suitable unalkylated or alkylated polyhalobisphenol may be used as one of the ingredients. The unalkylated and alkylated polyhalobisphenols may be represented according to their chemical structure as follows:

HO OH wherein X represents a halogen such as chlorine or bromine, n represents an integer of from 1 to 3, Y represents a divalent radical including alkylene radicals having from 1 to 4 carbons such as -CH CH CH -CH(CH C(CH CH CH CH etc.; halo-substituted alkylene radicals having 1 to 4 carbon atoms such as CHCl, CHBr, CHClCHCl, CH(CCI CH(CBr etc.; and S; and R in the case of alkylated polyhalobisphenols is an alkyl group containing from 1 to 4 carbon atoms.

The preferred compounds are symmetrical in structural configuration. Specific examples of the unalkylated polyhalobisphenols include 2,2-dihydroxy-3,5,6,3', 5',6',-hexachlorodiphenyl methane, 2,2'-dihydr0xy 3,5,3,5' tetrachlorodiphenyl methane, 2,2'-dihydroxy 4,5,4,5' tetrachlorodiphenyl methane, 2,2-dihydroxy 3,4,3',4' tetrachlorodiphenyl methane, 2,2'-dihydroxy-5,5'-dibromodiphenyl methane, 2,2'-dihydroxy 3,5,3',5' tetrachlorodiphenyl sulfide, 2,2'-dihydroxy-5,5'-dichlorodiphenyl sulfide, 2,2'-ethylidene bis(4-chlorophenol), 2,2'-ethylidene bis(6-bromo-4-chlorophenol) and 2,2'-(2,2,2-trichloroethylidene bis 6-bromo-4-chlorophenol Specific examples of the alkylated halogenated bis phenols include 2,2-dihydroxy 3,3 dimethyl-5,5'-dichlorodiphenyl sulfide, 2,2-dihydroxy-3,3'-dimethyl-5,5'- dichlorodiphenyltrichloro ethane, 2,2-methylene-bis(4- chloro 6 isopropylphenol), 2,2 methylene-bis(6-secbutyl-4-chlorophenol 2,2-ethylidene-bis( 4-chloro-6-iso propylphenol) 2,2'-ethylidene-bis(6-sec-butyl 4 chlorophenol), 2,2'-isopropylidene-bis(4-chloro 6 isopropylphenol), and 2,2'-isopropylidene-bis(6-sec-butyl-4-chlorophenol.

Used in conjunction with the unalkylated and alkylated halogenated bisphenols in the present invention are substituted carbanilides which can be represented by the following structural formula:

A Z A wherein A and B represent a halogen such as chlorine or bromine; A and B represent halogen, hydrogen and methoxy; and wherein Z is NHCONH,

NHCONHNHCONH-, NHCSNH NO ONE and NC ONH- 2H5 C H O Specific examples of the substituted carbanilide include 3,4,4 triehlorocarbanilide, 3,3',4 triehlorocarbanilide, 3,3',4-trichlorothiocarbanilide, 3,4,4 trichlorothiocarbanilide, 3,4-dichlorocarbanilide, 3,3',4,4'-tetrachlorocarbanilide, N-ethyl-3,4,4'-trichlorocarbanilide, 3'-bromo-3,4dichlorothiocarbanilide, 3 bromo-3,4-dichlorocarbanilide, 3,4-dichloro-4'-methoxycarbanilide, N-formyl 3,4,4 trichlorocarbanilide, and 1,6-bis 3,4-dichlorophenyl) biurea.

It has been found that when the unalkylated or alkylated halogenated bisphenols and the substituted carbanilides, as illustrated above, are used together in an antiseptic composition a germicidal effect is achieved which is greater than the mere total of the individual effects of the individual ingredients. This has importance in cases where the activity of the bisphenol is desired to be increased without employing higher concentrations, and in other cases, it assumes an even greater importance from an economic standpoint, since the presence of the substituted carbanilide enables a reduction in the total concentration of the germicidal agent while at the same time retaining the desired level of germicidal effect.

What the actual mechanism of the potentiating or synergistic eifect is, we are unable to explain. The invention relates to the synergistic cooperation of these two types of compounds when used in minor proportions in antiseptic compositions, especially antiseptic detergent compositions, and the discovery that this synergistic phenomenon occurs even at the high pH conditions existing in soap and detergent formulations provides one of the important phases of the present invention.

Relatively small amounts of the bisphenols and the carbanilides are sufiicient for the increased germicidal effect in the present invention. Satisfactory results can be obtained when the combined weights of the two agents are from 0.05% to 5% of the total weight of the composition. The objects of the invention may be achieved when the weight of the bisphenol is about 0.1 to 3% and the carbanilide is about 3% to about 0.1% of the soap or detergent weight. The preferred range is a weight concentration of about 0.25% to 1.75% of the bisphenol and about 1.75% to 0.25% of the carbanilide, and an excellent product is one containing soap and about 1% of each of the bisphenol and the carbanilide. It will be understood that even concentrations below the ranges just set out will provide some degree of germicidal effect and a substantially higher concentration than those referred to will provide satisfactory results, although there are certain practical considerations such as the cost of the bisphenols and a certain impairment in the detergent properties, which limits the desirability of greater amounts of the germicidal composition in the soap.

As indicated above, the ratio of the preferred range of the bisphenols to the carbanilide is about 1-7 of the bisphenol to about 7-1 of the trichlorocarbanilide, the parts being by weight. In other words, in a soap containing a germicidal concentration of hexachlorophene or bithionol, the substituted carbanilide is preferably used in the proportion of 1-7 parts to 7-1 parts of the hexachlorophene or bithionol.

The term soap refers to the water-soluble ammonium, metallic, or organic base salts of various fatty acids, which are chiefly lauric, oleic, stearic, and palmitic acids. As used in this description, the term is intended to cover all products in which soap is a major constituent, for example, bar, flake, powdered, soft and liquid soaps; shaving creams, toothpaste, cleansing creams, etc.

The invention also contemplates the use of anionic-type and non-ionic-type synthetic detergents in place of the soap. The anionic-type synthetics suitable for use in the invention can be described as those detergents having pronounced cleansing power and including in their molecular structure an alkyl radical containing from 6 to 18 carbon atoms and a sulfonic acid or sulfuric acid ester radical. Either organic base, ammonium, sodium or potassium salts of the anionic-type detergents can be used. The main types of detergents falling within this category are alkyl-aryl sulfonates, such as sodium or potassium dodecyl benzene sulfonate, sodium or potassium octadecyl benzene sulfonate, and sodium or potassium octyl naphthalene sulfonate; the alkyl sulfates, such as sodium or potassium salts of dodecyl, hexadecyl, and octadecyl sulfates; the sulfonated fatty acid amides, such as sodium or potassium salts of the oleic acid amide of methyl taurine; and the sulfonated monoglycerides such as the mono-coconut oil fatty acid ester of 1,2-hydroxy-propane-3-sodium sulfonate.

The non-ionic-type synthetic detergents suitable for use in the invention may be described as those detergents which do not ionize in solution but owe their Watersolubility to un-ionized polar groups such as hydroxyl or other linkages. The main types of detergents falling Within this category are the polyoxyethylene ethers of the higher fatty alcohols and alkyl phenols; the polyethylene glycols of fatty acids; fatty alkylol amide condensation products; polymers of ethylene and propylene oxides; compounds formed by the addition of propylene oxide to ethylene diamine, followed by the addition of ethylene oxide; fatty acid ethylene oxide condensation products; condensation products of ethylene oxide and a fatty acid ester of a polyhydric alcohol or sugar; and the detergents prepared by heating together a higher fatty acid with a diethanolamine. Some examples of synthetic non-ionics suitable for the purposes of this invention are ethylene oxide-tall oil fatty acid reaction products; isooctyl phenolethylene oxide reaction products; propylene oxide-ethylene oxide reaction products; and combinations of isooctyl phenol-ethylene oxide with coconut oil fatty acid-ethylene oxide reaction products.

The synergistic combinations of either the un-alkylated or alkylated halogenated bisphenol and the substituted carbanilides can be added to the soap or the detergent by any suitable method which results in a uniform distribution of the additives throughout the entire mass.

Specific examples illustrating the invention are set out as follows:

EXAMPLE I Antiseptic detergent compositions exemplary of the present invention were prepared by intimately mixing the ingredients listed in Table I below to form a composite containing 2% by weight active ingredient.

TABLE I Composition A B C D E Aliquots of each of the above-described compositions containing 2% by weight active ingredient were added to nutrient agar medium so as to give in each instance a concentration of 0.125 part per million of active ingredient in agar. The agar in each case was then poured into a Petri dish, allowed to harden and then streaked with a 24-hour old broth culture of M. nyogenes var. aureus diluted 1-10. The incubationin each case was at a temperature of 37 C. The degree of growth after a period of 48 hours is set forth in Table II, as follows:

moderate growth; 3+=Norma1 heavy growth.

6 aureus FDA strain 209. The plates were incubated 48 hours at 37 C. and the amount of growth in the plates noted. The results are given in Table I as follows:

Legend:

Materials used TABLE I G-l 1Hexachlorophene, 2,2'-d1hydroXy hexachloro d1- Composltlon A B C phenyl methane N eutral toilet soap containing about 20% by weight G52,2-dihydroxy tetrachlorodiphenyl methane $58353 )???5903f??? kififi flff n fflffif 98 98 hexachloro diPhenyl Sulfide 2,2'- 1iIi1hiydr0xy-3,3-dimethy1-5,5dichlorodiphenyl 2 TCC3,4,4-trichlorocarbanilide TCCA-3 3 4-trichlorocarbanilide -t hl b 1d TCC 2 1 no Omar am} e( S-l2,2'-th1ob1s(d1chloro d1methyl)phenol Aliquots of each of the above-described compositions Sodlum coco Soap, 80% Sodium tallow containing 2% by weight of active ingredients were added NomPmc detergent NnYlPhen1 P 9 moles ethylene to nutrient agar medium so as to give in each instance 9 a concentration of 0.15 p.p.m. of active ingredien in Amomc synthetlc detergent sod1um dodecylbenzene the agar. The agar in each case was poured into a Petri sulfonatedish, allowed to harden and then streaked with a 24-hour Amount of growth (M. pyogenes) on agar plates with broth culture of M. pyogenes var. aureus diluted 1-10. agar containing aliquots of the germicides incorporated The incubation period in each case was made at 37 C. in the following agents.

TABLE I Anionic Synthetic Water Soap Nonionic Detergent Detergent P.p.m. Total Germicide Basis Agar 0.6 0.4 0.2 0.1 0.6 0.4 0.2 0.1 0.6 0.4 0.2 0.1 0.6 0.4 0.2 0.1

CODE.-0=no growth on plates; 1=light growth; 2=moderate growth; 3=normal heavy growth.

for 48 hours. The degree of growth is set out in Table II EXAMPLE IV below:

TABLE II Antiseptic detergent compositions exemplary of the Composition: Growth present invention were prepared by intimately mixing the A 3+ ingredients listed in Tables I, II and III below t form a B 3+ 50 mposite C nta ning 0.5%, 1.0% and 3.0% respectively C by weight active ingredient.

l- N 1h th orm g 2+:Mode3ate g1 wtl i TABLE I 1+:Light growth +=Extremely light growth Thus is may seen that true synergism exists in the test described above.

EXAMPLE HI Both individual germicides and combination of germicides were incorporated in a soap containing 20% sodium coco soap and 80% sodium tallow soap, a non-ionic synthetic detergent and an anionic synthetic detergent, at a total concentration of 1% basis soap and 1% detergent solution prepared. Aqueous solutions of the individual germicides were also prepared at a concentration of 100 p.p.m. and further diluted to 10 p.p.m. The 1% detergent solutions were also diluted with distilled water to 10 p.p.m. total germicide. Aliquot amounts of these solutions were then added to liquid nutrient agar so as to give the concentrations of the germicide in agar in Table I below. Plates were poured, allowed to harden and streaked with a 24-hour broth culture of M. pyogenes var.

Composition A B C D E Neutral white toilet soap containing about 20% by weight of sodium coco soap and by weight of sodium tallow soap 99. 50 99. 50 99. 50 99. 50 99. 50 2,2-d1hydroxy-3,5,6,3,5,6

2,2 -dihydroxy-3,5,6,3 ,5 ,6

hexaohlorodiphenyl methane 2,2-dihydroxy-3,5,3,5-

tetrachlorodiphenyl sulfide 1 3,4,4'-triehlorocarbanilide TABLE III Composition Aliquots of each of the above-described compositions containing 0.50%, 1% and 3% respectively by weight active ingredient were added to nutrient agar medium so as to give in each instance a test concentration of 0.125 part per million of active ingredient in agar. The agar in each case was then poured into a petri dish, allowed to harden and then streaked with a 24-hour old broth culture of M. pyrogenes var. aureus diluted 1-10. The incubation in each case was at a temperature of 37 C. The degree of growth after a period of 48 hours is set forth in the following tables, in which Table I-A shows the results for Table I, Table II-A shows the results as to Table II, and Table III-A shows the results as to Table III:

TABLE I-A G-ll Bith plus plus G-ll 131th T T00 T00 Composition A B C D E Period of 1ncubation 48 48 48 48 48 Amount of Growth 1+ 1+ 3+ 0 0 TABLE II-A Composition A B C D E Period of Incubation 48 48 48 48 48 Amount of Growth 2+ 2+ 8+ 0 0 TABLE III-A Composition A B C D E Period of Incubation 48 48 48 48 48 Amount of Growth 2+ 2+ 3+ 1+ 1+ Legend.-- =No growth; 1+=Very slight growth; 2+=Light to moderate growth; 3+=Normal heavy growth.

The foregoing tests indicate that an excellent product is produced by the composition containing 0.5% of each of the active ingredients. All three soaps provided the activity shown in Tables I-A, II-A and III-A at the germicidal level indicated.

EXAMPLE V Experiments were carried out to determine the variation of synergistic effect with changes in the ratio of the component active ingredients. All experiments were carried out in a toilet soap medium. For this purpose the individual germicidal compounds or mixtures of compounds were incorporated at a total germicidal level of 1.0% into a conventional toilet soap base, obtained from the saponification of a blend of coconut oil and 80% in edible tallow. This was accomplished by passing a blend of the dry germicidal ingredient and soap chips (moisture content 11%) repeatedly over a three-roll laboratory soap mill until the blend appeared physically homogeneous. The blended soap chips were then dissolved in water to give a 1.0% soap solution, which corresponds to an 0.01% concentration of germicidal agent. Since some of the latter are not very water-soluble, these soap solutions were shaken before each test to insure a uniform suspension in water.

The bacteriological evaluations were carried out with a modified agar streak method. Aliquots of the 1.0% test soap solutions were added to measured amounts of liquid glucose tryptone extract agar, and the resulting mixture was poured into Petri dishes. As soon as the agar had hardened, its surface was streaked with a standard loop containing a 24-hour culture of S. aureus F.D.A. strain No. 209. After an incubation period of 48 hours at 37 C. the plates were examined visually, and the amount of growth was recorded.

In this manner a ratio study of the synergistic pair T.C.C. and hexachlorophene was carried out, the results of which are summarized in Table I. The analogous study of the pair T.C.C. and bithionol was carried out by using the same method, and the results of this study are summarized in Table H. The growth was rated and coded in the following manner: 0=no growth; 1=slight growth, where only a few sporadic colonies can be seen on the plates; 2=m0derate growth, where growth occurs along the streaks but one-half or more of the surface of the plate still shows little or no growth; and 3=heavy growth, where there is luxuriant growth over practically the entire surface of the plate.

CODE.0=NO growth; 1=Slight growth; 2=Moderate growth; 3= Heavy growth.

TABLE II Antibacterial Effectiveness of Varied Ratios of Bithionol and 3,4,4- trichloroearbanilide (T.C.C.) in Soap (Modified Agar Streak Method)] Bacterial growth ratings, total antibacterial agent at Ratio 0.1 ppm. 0.04 p.p.m.

20% T.C.C., Bithionol 10% T.C.C., Bithionol 0% T.C.C., Bithionol As indicated above, synergistic results were obtained when the ratio of the bisphenols (hexachlorophene or bithionol) to trichlorocarbanilide was between 90-10 parts by weight of the bisphenol to 10-90 parts by weight of the trichlorocarbanilide. In other words, the ratio was between 19 parts of bisphenol to between 9-1 parts of trichlorocarbanilide. The preferred range, as already stated, was between 1-7 parts of the bisphenol to 7-1 parts of the trichlorocarbanilide. In a soap containing a germicidal concentration of hexachlorophene or bithionol, we prefer to add trichlorocarbanilide in the proportion of between 1-6 parts to between 7-1 parts of the hexachlorophene or bithionol.

The results hereinabove set out with respect to a specific soap (20 coco and 80 tallow soap) are obtained with soaps generally. For example, any fatty acid soap will produce these results, such as sodium laurate, potassium stearate, sodium oleate, potassium myristate. The synergistic action is independent of the soap vehicles as shown by the activity of the ingredients in non-detergent vehicles and by their activity in anionic detergents other than soap and in non-ionic systems. At the same time, soap is a system in which the synergistic components are highly effective.

EXAMPLE VI Additional antiseptic detergent compositions exemplary of this invention were prepared incorporating 0.1% by weight of the following germicides in a 10% soap solution:

(1) 2,2 ethylidene bis (4 chlorophenol having the structural formula:

[Oi-i1 OH an. I i 01 Cl (2) 2,2 ethylidene bis (6 bromo 4 chlorophenol) having the structural formula:

OH OH (3) 2,2 (2,2,2 trichloroethylidene) bis (6 brorno- 4-chlorophenol) having the structural formula:

OH OH .Z Cl Br B. 01 A (4) 3,4,4'-trichlorocarbanilide.

In determining the germicidal activity of the above compounds, both alone and in combination with 3,4,4- t-richlorocarbanilide, the individual germicides and combinations of germicides at a 1:1 ratio were dissolved in dirnethylformamide at a 1.0% level. Then, suspensions of these germicides, both alone and in combination, in a soap solution were prepared. The total concentration of germicide in the soap solution was 1000 ppm. or 0.1%. Thereafter, serial dilutions were made containing 100, ppm. and 10 p.p.m. respectively of the germicides to be tested. The soap utilized in this test was a neutral white toilet soap containing about 20% by weight of sodium coco soap and 80% by weight of sodium tallow soap.

Varying amounts of the soap solutions containing the germicides to be tested were thoroughly dispersed into measured amounts of sterile liquid nutrient agar at concentrations ranging from .05 to 20 ppm. Plates were then poured, solidified, and streaked with a standard 4 mm. loopful of a 24-hour broth culture of Staphylococcus aureus strain FDANo. 209. After incubation for 24 hours at 37 C. the bacteriostatic end point was determined. This end point represents the concentration of germicide in ppm. (parts per million) necessary to completely inhibi-t growth.

The following table gives the end points of the minimum effective dose of 3,4,4-trichlorocarbanilide and the three polyhalobisphenols listed in subp aragraphs numbered 1, 2 and 3 above.

Test germicide: End point 3,4,4 trichlorocarbanilide 0.2 2,2-ethylidene bis(4-chlorophenol) 6.0 2,2 ethy-lidene bis(6 bromo 4 chlorophenol) 3.0 2,2 (2,2,2 trichloroethylidine) bis(6 bromo 4 chlorophenol) (1:1 ratio) 0.2

3,4,4 trichlorocarbanilide and 2,2 ethylidine bis(4- chlorophenol) (1:1) ratio) 3,4,4 trichlorocarbanilide and 2,2ethylidene bis(6- promo-4 chlorophenol) (1:1 ratio) 3,4,4 trichlorocarbanilide and 2,2'-(2,2,2-trichloroethylidine)-bis(6-bromo-4 chlorophenol) (1:1 ratio) EXAMPLE VII A series of substituted carbanilides and combinations of substituted carbanilides with hexachlorophene were incorporated in a soap containing 20% sodium coco soap and 80% tallow soap at a total concentration of 1% basis the soap. The ratio of substituted carbanilide to hexachlorophene was 50/50.

Aliquots of the individual soap preparations containing the substituted carbanilides, hexachlorophene and combinations thereof were added to liquid nutrient agar so as to give the concentrations in agar as set forth in Table I below. Plates were poured, allowed to harden and streaked with a 24-hour broth culture of S. aureus FDA No. 209. The plates were incubated 48 hours at 37 C. and the amount of growth in the plates was noted. The results are given in Table I as follows:

Amount of growth of S. aureus on agar plates with agar containing equal aliquots of one percent soap solutions.

TABLE I P.p.m. Total Germicide Basis Test Germicide Agar N 0. Individual 0. 2 0. 1

1 Hexachlorophene 0 1+ 2 3,4,4-trichlorocarbanilide.. 0 1+ 3 3,3,4-triehlorocarbanilide 0 1+ 4 3,3,4-trichlorothiocarbanilide 0 0 5 3,4,4-trichlorothiocarbanllide 0 0 6 3,4-diehlorocarbanilide 0 0 7 3,3,4,4-tetrachlorocarbanilide 0 0 8 N ethyl-3,4,4 -trichlorocarbanilide 0 0 9 3-bromo 3,4-diehlorothio carbanilide 0 0 10 3-bromo-3,4-dichlorocarbanilide 0 0 11 3,4-diehloro-4-methoxycarban' e 0 0 12 N-formyl 3,4,4-trlchloroearbanilide 0 0 13 1,6-bis(3,4-dichlorophenyl) biurea 0 0 Combinations 1 and 2 above 0 0 0 2+ 1 and 3 above... 0 0 0 2+ 0 O 0 3+ 0 0 0 3+ 0 O 0 3+ 1 and 7 above. 0 0 0 3+ 1 and 8 above 0 0 0 3+ land 9 above 0 0 0 3+ land 10 above 0 0 0 3+ land 11 above 0 0 0 3+ 1 and 12 above 0 0 0 3+ 1 and 13 above 0 0 0 3+ CODE.0=N0 growth; 1=Slight growth; 2=Moderate growth; 3= Heavy growth.

From the foregoing experiments it will be seen that the germicidal activity of the polyhalobisphenols is enhanced or synergized by the incorporation of certain substituted carbanilides.

While this invention has been described and exemplified in terms of its preferred embodiments, those skilled in the art will appreciate that variations can be made without departing from the spirit and scope of the invention.

What is claimed is:

1. An antiseptic detergent composition consisting essentially of soap and about one percent of a synergistic combination of 2-2'-dihydroxy-3,5,6,3,5',6-hexachlorophenyl methane and a substituted carbanilide selected from the group consisting of 3,3',4-trichlorothiocarbanilide, 3,4,4-trichlorothiocarbanilide, 3,4-dichlorocarbanilide, 3,3,4,4-tetrachlorocarbanilide, N-ethyl-3,4,4-trichlorocarbanilide, 3-brom0-3,4-dichlorothiocarbanilide, 3'- bromo-3,4-dichlorocarbanilide, 3,4-dichloro-4'-methoxycarbanilide, N-formyl-3,4,4-trichlorocarbanilide and 1,6- bis (3,4-dichlorophenyl) biurea, the ratio of said hexachlorophenyl methane to said substituted carbanilide being about 1 to l.

2. The composition of claim 1 wherein the carbanilide is 3,3,4-trichlorothiocarbanilide.

3. The composition of claim 1 wherein the carbanilide is 3,4,4'-trichlorothiocarbanilide.

4. The composition of claim 1 wherein the carbanilide 3,4-dichlorocarbanilide.

5. The composition of claim 1 wherein the carbanilide N-ethyl-3,4,4-trichlorocarbanilide.

6. The composition of claim 1 wherein the carbanilide is 3-bromo-3,4-dichlorothiocarbanilide.

7. The composition of claim 1 wherein the carbanilide is 3-brom0-3,4-dichlorocarbanilide.

8. The composition of claim 1 wherein the carbanilide is 3,4-dichloro4'-meth0xycarbanilide.

9. The composition of claim 1 wherein the carbanilide is N-formyl-3,4,4'-trichlorocarbanilide.

10. The composition of claim 1 wherein the carbanilide is 1,6-bis (3,4-dichlorophenyl)biurea.

11. An antiseptic detergent composition consisting essentially of soap and a combination of 2-2-dihydroxy-3, 5,6,3',5,6-hexachlorophenyl methane and a substituted carbanilide selected from the group consisting of 3,3',4- trichlorothiocarbanilide, 3,4,4'-trichlorothiocarbanilide, 3,4-dichlorocarbanilide, 3,3',4,4'-tetrachlorocarbanilide, N-ethyl-3,4,4'-trichl0rocarbanilide, 3,-bromo-3,4-dichlorothiocarbanilide, 3'-br0m0-3,4-dichl01'0carbanilide, 3,4- dichloro-4'-methoxycarbanilide, N-formy1-3,4,4'-trichlorocarbanilide and 1,6-bis(3,4-dichloropheny1)biurea, the ratio by weight of said hexachlorophenyl methane to said substituted carbanilide being about 1 to 1 and wherein said combination of hexachlorophenyl methane and sub- 12 stituted carbanilide display synergistic germicidal activity against S. aureus FDA N0. 209 when said combination is added to nutrient agar at a total concentration of 0.0-5 p.p.rn. basis the agar, said agar having been streaked with a 24-hour broth culture of S. aureus FDA No. 209 and incubated 48 hours at 37 C.

References Cited UNITED STATES PATENTS 2,535,077 12/1950 Kunz et al 252107 2,846,398 8/1958 Beaver et al. 252106 3,103,467 9/1963 Beaver et al 2521 07 X 3,177,115 3/1965 Casely et al. 167-30 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R. 252l06