US2937147A - Stabilized germicidal soaps and process of making the same - Google Patents

Description

W. soaps have to be marketed at a price ditferential pared toordinary soaps.

"STABIIVJVIIZEID GERMI'CIDAL som'mnimbcnss 1 OF MAKING THE SAME Seymore Goldwasser, Teaneck, NJ., assignorto Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Application September 28, 1955 Serial No. 537,301

16 Claims. (Cl.. 252107) This: invention relates to a process for the preparation of germicidal detergents and to germicidal detergents obtained by this process and more particularly to detergent compositions which combine the detergent properties of ordinary soaps and nonsoap detergents" with the germicidal properties of N-substitut'ed thiuram sulfides, and to a process of preparing such detergents.

The normal. human skin is the habitat of millions ofa bacteria, the majority-of which are beneath the surface of the skin. Of the forty million bacteria usually found .on and in the skin of the two hands and arms to the elbows, only about one million arevtransients residing on the skin surface; the remainder areresident bacteria and 1 reside iii-subsurface skin layers. Transient bacteria are readily removed mechanically hy ordinary soap. Resident bacteria are usually removed only following attack by a satisfactory degerming agent, whose effectiveness is due to its absorption by the skin, so that it is available "to act continuously on bacteria present in the subsurface layers, thereby preventing their multiplication to any appreciable degree. 7

It is for this reason that germicidal'soaps which have eagerness ray, 17-, 19 0 2 view of the very considerable research which led'to the development of these compounds, the discovery of another germicide which could be combined soap would be quite unexpected. V

In accordance with. the instant invention, a germicidal detergent soap is provided comprising as a germicidal agent a thiuram sulfide having each thiuram nitrogen atom fully substituted with aliphatic groups, and a peroxide which acts as a stabilizer for the thiuram sulfide. I

At concentrations appreciably less than would be used in the case of hexachlorophene (2',2 '-dihydroxy-3,5, 6-

3,5',6-hexachloro diphenyl methane); suchthiuram sulfides are capable of producing germicidally potent soap compositions. V

The compositions of the invention are more active against gram-negative organisms such as Escherichia coli than hexachlorophene soaps and are more substantive to the skin than hexachlorophene soaps. The soaps of the invention lack otfensive'odors. The low cost and availability of these thiuram sulfides favorably distinguish them from other germicides.

The term thiuram sulfide is inclusive of thiuram monosulfides, disulfides, trisuliides, tetrasulfides and hexasulfides.

The aliphatic thiuram sulfides used as a germicidal' agent in the soap compositions of the invention have the,

following formula:

a t-W1 v 1 s s n has the value of one to six, and Z and Z each are selected. from the group consisting of a single bivalent cycloaliphatic radical and two monovalent aliphatic radicals. The number of carbon atoms is not critical, but

the antibacterial activity tends to decrease as the number recently been placed on themarketj-havev found a wide application. Such soaps contain a'small amount of a germicidal agent and the use of the soap in daily washings provides suflicient germicide to keep the bacterial count. ..at a practical minimum. In fact, the'bacterial Y 1 count can be lowered to a point at which it equals or "is even lower than that produced-by the surgeon through 't'hei'application of the standard 'hospitalnscrub-up techm ae; "Hexachlorophene: r: (-2,2'-.- dihydroxy,-.3,5,6-3',5,6T-

1 hexachlorodiphenylv methane) has been proposed .for. I use in} soap. Thissubstance, however, in common with other 2, 2="-dihydroxyhalogenateddiphenyl methanes, has a low potency 'atullow' concentrations. It: not very elfective againstgrant-negative organisms such as Escherichia coli.

Soaps containing hexachlorophene tend to darken in daylight, and may have or. develop an 'objectionableodor which lessens the attractiveness. of such soaps to the consumer. Moreover; 2;2-:dihydroxy halogenated diphenyl methanes are expensive chemicals, and since fairlyrlarge amountsl tox3-% basisfsoap weight) are needed for eli -ec'tive germicidal action, hexachlorophene germicidal 00111 th es,-.various--phenolic materials have'been combined ap;- but because of the generally recognizedtde action of. soapupon the bactericidal. properties- 5 5 gerr'nici'rlal agents, germicidal soapsj -have not; been staine V by Kunz and Gump and is reviewed in some detail at columns 3' and 4 of their US. Patent No. 2,535,077,

. dated December 26,- 195 0; Althoughfthe 2 ;2f-'d'iliydroxy ha'l ena'ted diphenyl"methanes iare'wantingfin some r sp'e they have" been recorded-as" unique in that their inaddition to -the=2;2"-dihydroxy' halogenated diphenyl This point-hasbeen etfectively demonstrated I fgiirrhicidal potency is relatively'jiinaifected by soap. In I of carbon atoms increases, and therefore Z and pref erably have from two to eight carbon atoms.

When 2, and/ or Z are bivalent, taken with the thiuram nitrogen atom they form a saturated or unsaturate d heterocyclic ring in which the thiuram nitrogen atoinzis 1 p A typical heterocyclic radical of one of the ring atoms. this type is piperidine.

'When Z 'and/or Z are monovalent they can be selected from the group consisting of saturated and unsaturated straight and branched chainfaliphatic radicals, preferably having from one to four carbon atoms.

Among those which can be employed areiethyl, methyl, 1

propyl, isopropyl, n-butyl, isobut-yl,v tert.-butyl, sec.-butyl,

butadiene, butylene and propylene. Alkyl radicals hav- 5 ing from one to two carbon atoms are preferred;

Typical aliphatic thiurammonosulfide's {coming within the invention are:

effectively with Typical aliphatic thiuram disulfides coming within the invention are:

A typical thiurarn tetrasulfide coming within the invention is:

The aliphatic thiuram'sulfides are known classes of materials, andtheir preparation is set forth in the literature. Forthemost part they are insoluble in water, soluble in alcohol, acetone and benzene, and very soluble in chloroform and carbon disulfide. In the quantities in which they are employed in soaps,.they do not produce skin irritation, are not toxic, and are compatible with the usual soap components, including neutral salts, perfume, opacifiers and small amounts of carbonates.

The term soap as used herein refers to alkali metal soaps of the saturated and unsaturated higher fatty acids having from' about eight to about twenty-six carbon atoms, such as. capric, caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, arachidic, behenic, margaric, tridechoic, and cerotic acids and themixtures of such acids naturally occurring infats, oils, waxes, and rosins, such as the soaps of coconut oil fatty acids,,ta1low fatty acids, pig fat, fish oil fatty acids, beeswax, palm oil fatty acids, sesame .oil fatty acids, peanut oil fatty acids, olive oil fatty acids, palm kernel oil 'fatty acids, cottonseed oiliatty'acids, soyabean oil fatty acids, corn oil fatty acids, bab,assu oil fatty acids, rosin acids, abietic acid, and greases,

Only small amounts of thiuram sulfide are required to render soap germicidaL; -An amount as low as 0.01% based on the weightof the soap produces a soap composi tion having excellent antibacterial potency. As much as 5% has been used to advantage. There is no need to to the thiuram sulfide.

. which the soap is formed, e.g.,

employ more than is required to give'the desired germicidal eifect, and in general for this reason from 0.2 to

2.0% would :be. preferred. Increasing the concentration of thiuram sulfide beyond 5% further increases the costof the soap and might tend to reduce the detergent properties of the composition. 'At unnecessarily high concentrations there is a possibility of skin irritation due It will readily be seen that the thiuram sulfide concentrationnot critical but would be determined from a consideration of these factors, as

long as enough is used to give the desired antibacterial effect;

When exposed to high temperatures for long periods of time or over long periods of storage even at ordinary temperatures thiuram sulfide in a soap composition shows a tendency'to decompose. The decomposition products are unknown but appear to include complex sulfur compounds, amines, carbon disulfide, and mercaptans. These materials lead to the development of an undesirable and in some cases an exceedingly unpleasant odor. Reactive sulfur-bearing compounds appear also to be available, because if a soapcontaining the decomposition products of thiuram disulfide comes into contact with copper ion 'a dark colored sulfur compound of copper is formed, insoluble in Water, resulting in a darkv colored stain Which can be removed by customary cleaning methods or by treatment with acid but Which it is desirable to avoid if possible. In accordance with the invention, therefore, there is incorporated in the thiuram sulfide soap composition aperoxide whichacts as an inhibitor against the {*decomposition ofthe thiuram sulfide.

' I The term peroxide is inclusive of any organic or inorganic compound which forms hydrogen peroxide in alkaline solution, for example, sodium perboate, sodium pyrophosphate peroxide, v'lauroyl peroxide, benzoyl perox- ..-ide, and sodium persulfate.

The organic peroxides are preferred'because they leave no salt residue upon decomposition. A

. In general, it can be said that any amount of the peroxide Will improve the stability of the thiuram sulfide soap against odor and staining, and the amount which would be employed therefore will depend upon the storage stability which is required. It may be observed that in the cases where the soap, because of prior processing r'nethods',contains reducingagents, for example, hydrosulfit'e added in the kettle to bleach {the soap, it is neces- ;sary to employ a supplemental amount or the peroxide to function as an oxidizing agent to destroy such reducing agents.

There is no upper limit to the .amouritotperoxide j which can be used. Amounts within the range of 0.05 to' 2% have been found to give adequate inhibition of odor formation and staining, but as much as 5% is not disad- "vantageous, although usually unnecessary and therefore not economical. Even more than 5% can be. used.

It has been found that free alkali must be eliminated from the thiuram sulfide-peroxide-soap composition. This may be accomplished, if the peroxide is acidic, by addition of a sufficient additional amount of the peroxide where necessaryto take up all of the free alkali. If the peroxide is notacidic, then free acid is added in the amount required to take up allof the free alkali. As the acid, there can be used an. inorganic acid, such as boric acid, or an acidic inorganic salt, such, as sodium bicarbonate, or an organic acid, including the long and short chain aliphatic acids, especially the free soap. acids of stearic, myristic, and palmitic'acids, or mixtures of any of these. i

When aperoxide is incorporated in these soap compositions, it is important that all of the ingredients be added before the thiuram sulfide, and that the thiuram sulfide be thoroughly dispersed in the soap mixture. Mixing of the batch should not be continued beyond the point at which the thiuram sulfide is thoroughly dispersed. I

While several mixing; procedures will be apparent mi those skilled in the art in order to achieve thisrc sult, the

following procedureis-recommended: T he soap chips are weighed into the mixer and fol-lowed immediately by addition of the peroxide. Theperoxide cansbeadded in the form of a solution 'or dispersion in water,= i rrwhich the concentration of the peroxide is not critical,- 1 'MlXlIlg is continued for a sufiicient time to insurethorou'gh" dispersion. of. the peroxide in'the soap. The remaining components of the mix, for example, perfume and dye, are added, in the form of. a solutionif. desired, as quickly as possible and mixing is continuedagain fora long enough period to insure a thorough dispersion. Thereafter the thiuram sulfide is added with. complete and'adequ'ate mixing only for the timeto insure uniformity? of .disper- The final mix then' can be treatedin the maven--- sion. tional ways to produce the desired soap. To. form a bar, for example,- the mix can be plodded and extruded using conventional equipment.

The thiuram sulfide soaps in accordance with the in v I vent-ion can be formed-as bar soaps, powered soaps, chip; soaps, flake soaps, bead soaps, bar andcakesoaps and soap compositions intended for toilet, washing'an'd disinfectant purposes in addition to their use as detergents.

The compositions canbe dried in. any desired way;-spray drying is convenient in many instances. It is desirable to hold the temperature to which the .mix is-subjected during conversion intoits final form belowthe tempera ture at which the thiuram sulfide would be decomposed. Soap mixtures'in accordance with the invention have been subjected to temperatures up to-'I25' F. for'periodsof up to one hour without disadvantage. V

The germicidal effectiveness of the soap compositions of the invention has been measured by theSerial Basin iv dividual subjects are used as a panel in each test. Two types of soap are usedin the test, the germicidal soap employed daily for the two Week test period andthe plain soap used where the wash water is collected in various basins for determining the counts of bacteria removed;

The subject exposes the armsuptotheelbow, and 2000 cc. oflukewarm tap water are run into the sterilized first i p basin, the bacterial count-of the water .beingdetermined I byre'moving two lj'cc. samples 'which ar'e adde 18cc. oflnutrient" a ar; subject mo upto the wristline, thenapplies plain: soap for 'fifteen'secg g' 1 ends followed by thorough latheringfor sixty's'econdsk The. hands are rinsed thoroughly the basin. 1

Two more similar washings are carried out successively under the tap, the area. covered extending almost to the elbows, and the Water is discarded.

The subject then moves to the second basin containing 2000 cc. of lukewarm tap water and carries out the washing procedure exactly as in the first basin. i i

for fifteen. seconds into The subject then moves to the third basin 'andrepeats Y V the washing procedure of Basins 1 and 2.

Two 1 cc. of samples of 2000 cc. wash water each 4 basin are removed using 'a sterile pipette'and added'to 15 cc. of nutrient agar in sterile Petri dishes. This is agitated, allowed to cool and harden and incubate at 37 C. for forty-eight hours. At the end of this time'the nuni= i ber of colonies present are counted and the.counts multiplied by 2000.

The above test is repeated at intervals over the two weeks test period. The percent reduction 1 in bacterial count is computedon the basis of the reduction in count of the 2nd and 3rd, basin wash waters.

(2) The Zone Reduction Test.-This test measures the inhibitory eifect of an 8% solution within the zone of direct contact of the solution with the bacteriaseeded agar. A range of dilutions is investigated to determine the minimum concentration of germicide in the soap solution required to effect a strong reduction in the bacterial count in the agar in direct contact therewith. An 8% 1 solution of the soap is used since this is approximately the concentration of soap found in lather.

. For use in the test, cultures of Staphylococcus aureus and Escherichia coli are maintained on nutrient broth with transfers made daily. In preparing the agar plates, 0.1 ml. of a twenty-four hour nutrient broth culture of the test organism is mixed thoroughly into 15 ml. of melted nutrient agar, which is then poured into a Petri plate and permitted to harden.

Filter paper discs (0.5 inch in diameter) prepared from Whatman Filter Paper No. 2 are placed on the hardened agar circularly (about 0.75 inch from the periphery).

Each disc is wetted carefully with one measured drop of the 8% solution of a test soap, using a syringe (25 gauge needle). Six or seven discs can be arranged on each seeded agar plate, including the control plain soap. Duplicate plates are prepared and are incubated for twenty-four to forty-eight hours at 37 C.

In counting the plates, the filter discs are carefully removed with forceps and the zones of disc contact are examined microscopically (100x) with replicate counts made of fields selected at random. To facilitate counting, a Howard Micrometer Disc (No. 823) can be inserted into the ocular piece (10X); five fields of three adjacent squares are counted and the average field count determined.

The antibacterial potency of a test soap solution is expressed in terms of a Bacteriostatic Index which is computed from the average zone readings as follows:

Bacteriostatic index Av. zone count of test soap X100 Av. zone count of control soap Index:

8S-no antibacterial activity 60-85slight 30-60-moderate 30--strong --very strong 1 Basis soap weight.

for fifteen minutes. At the end of this time, the soap solutions are drained from the discs and sterile water added. The discs in the sterile water are shaken for fifteen minutes with a frequent change of water and then placed on the inoculated agar as in the Zone Reduction Test.

The compositions prepared in accordance with the invention have shown excellent germicidal effectiveness when subjected to these tests.

The following example illustrates the invention:

Soap chips (750 lbs.), formed from a charge of tallow and 20% coconut oil, bleached by the addition of sodium hydrosulfite Na S O and containing 0.05% free alkali, were weighed into the mixer, following which 1 lb. 8 oz. of lauroyl peroxide was added at once. Mixing was continued for five minutes after which 5 lbs. 13 oz. of perfume and dye were added over a period of one minute and mixing continued for three minutes. Tetramethyl thiuram disulfide (7 lbs. 11 oz.) was added by spreading it over the surface of the mix and mixing was continued for not more than four minutes. At the end of this time the tetramethyl thiuram disulfide was found to be thoroughly dispersed in the soap. The mix was transferred to a refiner where it was extruded through screens into another extruder and then into a plodder and formed into bars, all at temperatures between and F.

Any of the above-mentioned thiuram sulfides and/or peroxides can be substituted for the tetramethyl thiuram disulfide and lauroyl peroxide with satisfactory results.

The soap bars obtained were packed in an inner wrap of glassine paper and an outer carton of white patent coated board and subjected to storage at ordinary room temperatures for nine months. No change in the product was noted, whereas in the case of a soap containing thiuram sulfide but no lauroyl peroxide prepared exactly as set forth, yellowing of both the glassine and the board was observed, due probably to sulfur compounds formed by decomposition of the tetramethyl thiuram disulfide. The aged product containing the lauroyl peroxide had no odor and did not produce stains in the presence of copper ion, whereas the product which did not contain the lauroyl peroxide did produce such stains and had a strong odor.

It has been postulated that the decomposition of the thiuram sulfide which leads to the difliculties noted above follows the following course:

The carbon disulfide, .dimethylamine and other decomposition products ofdithiocarbamate, would be responsible for an ofi odor in the product.

A reducing agent such as hydrosulfite or sulfite might react in a similar fashion:

9 a t I From'Equation it can beseen thatbnemoIecuIe of hydrosulfite can be responsible for thdecompositiohto the ditliiocarbamate state of three molecules of tetramethyl thiuram disulfide and that thedeoomposition is i very sensitive to hydroxyl ion.

, any aqueous solution in the presence of a reducing agent.

"(Germs or bacteria may act as reducing agents.) In use it is not clear Whether the-germicidal properties of the soap" are 'due to the thiuram sulfide or to the dithiocarbamate, but it is not important to establish this since both' are present in soap solutions. Dithiocarbamate has been found to enjoy but a transitory existence in" soap compositions, and thereforein order to preserve its activity in soap solutions which are subsequentlypr'e- I pared from the compositions, should it be the germicidal agent in thelsoap solution as used, the thiuram sulfide is kept from forming the dithiocarbamate in the soap,

but not in the solution, by the'peroxide of. the invention.

, t The free alk ali is determined in accordance with the following procedure: The soap, befor'e' addition of dye, thiuram sulfide and stabilizing-agent, is weighed outin a 250ml. extraction flask on atriple beam or torsion balance, 12.4 gms. in the case of soap chips or fine soap, i.e., soaps of higher fatty acids, 31 gms. in the case of framed soaps and pan samples, i.e., soaps of about 63% fatty acids. To the soap is added approximately 100 ml. of neutralized alcohol and several glass beads and the soap is dissolved completely in'the alcohol by boiling gently on a hot plate under a reflux air condenser. One ml. of phenolphthalein indicator is added and the solution titrated while hot to the disappearance of the phenolphthalein color. N/4 solutions are used for framed soaps and pan samples, and N/ solutions for soap chips and hue soaps. The color change is not very defiinitc for the latter and is recognized in a change of color rather than a disappearance. A blank determination is made on 100 ml. of the neutralized alcoholcfor each batch when N/10 solutions are used, and the volumes of acid or alkali required for neutralization are noted. The calculation then is carried out according to the following equations: For soap chips and fine soaps: I v Ml. N/lO acid correctedlx 0.0031 x 1.00 a 12.4

=percent; Na O Ml. N/10 aoid 0.025=percent Na i) For framed soapsand pan samples: Ml. N/4 acidX 0.00775 10o 31 i =percent N320 Ml. N /4 acid 0.025=percent Na O The compositions of the invention meet all of thererecommended for uses in which both detergent and degerming characteristics are desired. The test results show that the compositions used routinely for a period of from one to two weeks lower the bacterial flora of the skin to, a very low level, equivalent to that obtainable by means of the standard hospital scrub-up operation. The compositions are particularly valuable for routine surgical and hospital use and generally useful in the prevention of infections arising from skin bacteria.

Those skilled in the art will perceive manyvariations 7 in the compositions of the invention. For example, the

aliphatic thiuram sulfide need not be the only germicidal composition against decomposition of thiuram'sulfide as evidenced bythe development of odor andstaining. charagent; other germicides, such as ,2',2' -dil iydroxy"halo genated "diphe'nyl methanes, can be included, for ample, if desired. The soap compositions, in addition to the soapand germicide, will also usually contain fillers; coloringmaterials and perfumes, as desired, as is familiar to-those skilled in the art. V r

The compositions containing the thiuram sulfidejmay contain mixtures of detergents, such as soap andah' anionic nonsoap, or soap and a nonionic nonsoap. Typical satisfactory anionic nonsoaps are the alkyl sulfates,

typified by sodium lauryl sulfate, known in the trade as Duponol C, the alkyl aryl' sulfonates, typified bythe sodium polypropylene benzene or t'oluene sulfonates', and the sodium keryl benzene or toluene sulfonates, the sulfated ethoxynated phenols, typifiedbythejamnionium salt of sulfated ethoxynatednonyl phenol; prepared by a condensation of nonyl phenol with live moles ofethylene oxide, and the sodium fatty acid esters of taun'ne,typitied by sodium palmiti'c or oleic' methyltauride or mixtures thereof, and the esters of higher" fatty acids and hydroxy ethane 'sulfonates such' as oleic acid: ester of hydroxy ethane sodium sulfonate. Also useful'are nonionic nonsoaps, such, as the"'polyethylene, glycol esters of thehigher fattyacids, typifiedby po'lyoxyethylene ethylene'tand propylene glycol ste'arates, the polyethylene glycol ethers of alkyl phenols, typified by the condensation product of octyl and nonyl phenol with five, to twelve moles of ethyleneoxide; and the higher fatty acid esters of sorbitan-ethylene oxide condensates, such as s'orbitanmonostearate ester ofjpolyoxyethylene glycol. Theymay bein any of the-forms described here tofore, including cakes or powders, and may include various fillers, sudsing agents and ingredients conventionally employed in detergent formulations, They may be compounded for various purposes, such as for shampoo, dishwashing, textile laundering, toilet soap and similar preparations.

The thiuram sulfide may be included in compositions which contain soap or other surface active agents not intended primarily for detergent use, suc h' as various.

powdered cosmetics.

All percentages in the specification and claims are by weight of the soap.

This application is a continuation-in-part of-application Serial No. 397,001, filed Decemberf 8,1953, nowv abandoned. 1 p I claim: 1. A germicidal detergent composition amount of a thiuram sulfide having the formula:, T

r el- 2 S S a where n is an integer from one to six and Z and Z are hydrocarbon radicals having from two to eight carbon atoms and are selected from the group consisting of a single bivalent cycloaliphatic radical and two monovalent aliphatic radicals, and a peroxide characterized by forming hydrogen peroxide in alkaline aqueous solution, said i peroxide being in an amount to stabilize'the detergent acteristics.

2. A germicidal detergent soap comprising soap suba stantially free from free alkali, a peroxide characterized a by forming hydrogen peroxide in alkaline aqueous solustantially free from free alkali, a peroxide characterized '7 substantially free from tree alkali comprising soap; a germicidal f 11 by forming hydrogen peroxide in alkaline aqueous solution, and a germicidal amount of N-tetramethyl thiuram monosulfide said peroxide being in an amount to stabilize the detergent composition against decomposition of ,thiuram sulfide as evidenced by the development of odor and staining characteristics.

4. A germicidal detergent soap comprising soap substantially free from free alkali, a peroxide characterized by forming hydrogen peroxide in alkaline aqueous solution, and a germicidal amount of N-tetramethyl thiuram disulfide said peroxide being in an amount to stabilize the detergent composition against decomposition of thiuram sulfide as evidenced by the development of odor and staining characteristics.

5. A germicidal detergent composition in accordance with claim 1 in which the thiuram sulfide is present in an amount within the range from 0.01 to about 5%.

6. A germicidal detergent composition in accordance with claim 1 in which n has the value of one.

7. A germicidal detergent composition in accordance with claim 1 in which n has the value of two.

8. A germicidal detergent composition in accordance with claim 1 in which the peroxide is lauroyl peroxide.

9. A germicidal detergent composition in accordance with claim 1 in which the peroxide is benzoyl peroxide.

10. A process of forming a germicidal detergent composition comprising dispersing in soapa peroxide characterized by forming hydrogen peroxide in alkaline aqueous solution, said peroxide being in an amount to stabilize the detergent composition against decomposition of thiuram sulfide as evidenced by the development of odor and staining characteristics, and then dispersing therein a germicidal amount of a thiuram sulfide having a formula:

where n' is an integer from one to six and Z and Z; are hydrocarbon radicals having from two to eight carbon atoms and are selected from the group consisting of a single bivalent cycloaliphatic radical and two monovalent aliphatic radicals, including adding an acidic compound if necessary to eliminate free alkali and form a composition substantially free from free alkali.

11. A process in'accordance with claim 10 in which the peroxide is acid-reacting, and is added in an amount to eliminate free alkali in the final composition.

12. A process in accordance with claim 10 in which the acid-reacting compound is an inorganic acid.

13. A process in accordance with claim 10 in which the acid-reacting compound is an inorganic acid-reacting salt.

14. A process in accordance with claim 10 in the acid-reacting compound is an organic acid.

15. A process in accordance with claim 10 in which the peroxide is lauroyl peroxide.

16. A process in accordance with claim 10 in which the peroxide is benzoyl peroxide.

which References Cited in the file of this patent UNITED STATES PATENTS Re. 22,750 Tisdale et al. Apr. 30, 1946 1,278,518 Tanaka Sept. 10, 1918 1,791,876 Somerville Feb. 10, 1931 1,824,809 Flammer et a1. Sept. 29, 1931 2,695,881 Elliott et a1. Nov. 30, 1954 OTHER REFERENCES British Medical Journal, June 17, 1944, article by Gordon et al., pp. 803-806.

Claims (1)

1. A GERMICIDAL DETERGENT COMPOSITION SUBSTANTIALLY FREE FROM FREE ALKALI COMPRISING SOAP, A GERMICIDAL AMOUNT OF A THIURAM SULFIDE HAVING THE FORMULA: