US2931777A - Germicidal detergent compositions - Google Patents

Description

' agents.

United States Patent '9 "ice GERMICEAL DETERGENT COMPOSITIONS Herman Alder Shelanski, deceased, late of Philadelphia. Pa., by Bessie Shelanski Rosen, executrix, Philadelphia, Pa., and by Harry Fair, Philadelphia, Pa., trustee, assignors to General Aniline 8: Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Application August 16, 1956 Serial No. 604,574

4 Claims. (Cl. 252 -106 This invention relates to an improved detergent composition comprising a mixture of a water-soluble nonionic surface-active agent containing a polyglycol ether group and a germicidally effective amount of iodine. This application is a continuation-in-part of application Ser. No. 163,082, filed May 19, 1950, now abandoned.

It has been found that the nonionic surface-active agents which contain a polyglycol ether group readily dlSe action now makes this combination not only an efficient one, but one which is to be recommended from the economic standpoint.

It has been found that the combinations of elemental iodine with these nonionic surface-active agents are particularly desirable in that a stable product is obtained which is effective in the dilute solutions normally used for cleaning operations, particularly, in food handling plants and institutional cleaning. The iodine is readily incorporated in these nonionic surface-active agents by merely adding the iodine to these nonionic. surface-active It'has been found that ordinary iodine crystals will dissolve by merely being allowed to stand in the nonionic surface-active agent. However, solution may be expedited by grinding and stirring the iodine in the nonionic surface-activeagent. Up to 15% of iodine has been readily added to the nonionic surface-active agent and larger amounts apparently can be added, but are not necessary. The solution was found to be stable on storage. The amount of iodine to be added to the nonionic surface-active agent will depend on the intended use of the product, since obviously, with products intended for use at high dilutions, more iodine must be present in order to have effective bactericidal effect than in products intended for use at lower dilutions. However, the amount of iodine required in the final solution used in any given ,the composition might be increased, but would still be less than the quantity of iodine alone required to accomplish the same effect.

it has been found that as little as 1% iodine dissolved in these nonionic surface-active agents is effective when the composition is employed in the range of dilution normally used for cleaning, and the bactericidal effect of the iodine is substantially enhanced. Thus 1% solutions of iodine in these nonionic surface-active agents were tested against Staph. aureus in the usual phenol co-efli- 2,931,777 Patented Apr. 5, 1960 cient tests. It was found that with this composition at dilutions of 1:60,000 iodine, and roughly 113000 nonionic surface-active agent, complete kill was effected in 5 minutes; while, at dilutions of 1:80,000 iodine, complete kill was effected in 10 minutes. As compared with this in the same test, using Lugols solution, complete kill was effected at 5 minutes at iodine dilution of 125,000,. and in 10 minutes at a dilution of 1:40,000.

EXAMPLE I 1 gram of iodine crystals were added to 99 grams of a commercial water-soluble nonionic surface-active agent obtained by condensing 8 to 9 molar proportions of ethylene oxide with 1 molar proportion of nonyl phenol (which, in turn, had been produced by reacting propylene trimer with phenol) as described in Example 8 of US. Patent No. 2,213,477. This nonionic surface-active agent was an essentially colorless viscous oily liquid.

The resulting mixture was stirred in a mortar and pestle until the iodine crystals were completely dissolved. The thus obtained product, comprising iodine combined with the water-soluble nonionic surface-active agent was a dark brown (mahogany) viscous oily liquid. It had no iodine odor and no color developed on moist starch paper held over it. It was, however, titratable for iodine with sodium thiosulfate. The product was tested against Staph. aureus in the usual phenol co-efficient test. At dilutions of 1:60,000 iodine, complete kill was effected in 5 minutes, while at dilutions of 1:80,000, complete kill was effected in 10 minutes.

As indicated above, up to 15% of iodine can readily be incorporatedin the nonionic surface-active agents, and the exact amount which should be incorporated de pends on the germicidal activity which is desired, and on the concentration'at which the mixture is to be used. For generalpurpose detergent, for household and similar use, from 1 to 3% of iodine, based on the amount of nonionic surface-active agent produces a composition having effective bactericidal action when used in dilutions of the order of 1:3000.

Not only does the mixture of nonionic surface-active agent and iodine have a synergistic bactericidal effect, but it has been found that the vapor pressure of the iodine in the solution is reduced to substantially zero, since the mixture has no odor of iodine, and, on heating the mixture, the starch test is negative. In addition, it was found that the skin irritation and sensitization effects of the iodine were eliminated from the mixture. Skin patch tests on known iodine sensitive individuals were negative with the mixture, whereas they showed 4+ and higher reactions to Lugols solution. The mixture can be used in contact with white cotton materials which contain starch without any discoloration of these fabrics even in dilutions ad infinitum. Yet, the quantity of iodine can be determined volumetrically on titration with sodium thiosulfate at any dilution. Further evidence of the stability of this mixture is shown when dilutions of the mixture are passed through carbon filters, none of the iodine is removed.

The liquid, non-ionic, polyglycol other type surfaceactive agents which are useful for producing the novel compositionsof this invention are the normally liquid, non-ionic, surface-active agents obtained by condensing alkylene oxides with water-insoluble organic compounds containing at least six carbon atoms and having an active hydrogen, such as organic hydroxy compounds, i.e., alcohols, phenols, thiols, primary and secondary amines, carboxylic and sulfonic acids and their amides. Compounds of this type are well known in the art, and are disclosed along with suitable methods for their preparation, in ,U.S. Patents Nos. 1,970,578, and 2,213,477.

"ape-1,777

They may be represented by the following general formula:

wherein R represents the residue of an organic compound containing an active hydrogen and the R represents hydrogen or lower alkyl, and n represents an integer of from 3 to 100 or higher, and usually from 6 to 50. These compounds may readily be obtained as disclosed in the above-mentioned patents by condensing a polyglycol ether containing the required number of alkenoxy groups, or an alkylene oxide, usually ethylene oxide ('although propylene or butylenejoxides may be employed if desired) with a water-insoluble-organiccompoundfcontaining at least 6 carbon atoms and having an "active hydrogen. The amount of alkylene oxide condensed with the water-insoluble organic-compound having fan active hydrogen, i.e., the length of the polyglycol ether chain, will depend primarily on the particular compound with which it is condensed. As a convenient rule of thumb, approximately 1 mole of alkylene oxide should be employed for each two carbon atoms in the waterinsoluble organic compound containing an active hydrogen with which it is condensed. However, the optimum amount of alkylene oxide can readily be determined in any particular case by preliminary test.

The liquid, nonionic, polyglycol ether type surfaceactive agents derived from alkyl phenolic compounds have been found to be particularly valuable in detergent compositions, and, therefore, the polyalkylene oxide derivatives of such phenolic compounds are a preferred type of nonionic surface-active agents which are employed in the compositions of the present invention. Numerous compounds of this type, i.e., polyalkylene oxide derivatives of phenolic compounds containing one or more alkyl substituents, which may be employed in the compositions of the present invention are described in U.S. Patent No. 2,213,477, and preferably, employ the water-soluble poly-alkylene oxide derivatives of alkyl phenolic compounds in which the total number of alkyl carbon atoms is between 6 and 18. As examples of such phenolic compounds may be mentioned the isomeric dibutyl and diamyl phenols and cresols, tripropyl phenol and cresol, secondary or tertiary isomeric heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, cetyl, oleyl, oetadecyl, and the like, phenols and cresols. Of particular value are the polyalkylene oxide derivatives of secondary and tertiary alkyl substituted phenols and cresols obtained by condensing olefines of the type obtamed in petroleum refining with phenols or cresols. In the case of products obtained by condensing phenol or cresol with olefines of from 3 to 5 carbon atoms, such as, propylene, butylene and amylen'e, it is desirable to employ the dialkylated phenols, or cresols; while, in the case of compounds obtained by condensing a phenol or cresol with an olefine containing 8 or more carbon atoms, the mono-substituted derivatives are preferred. Particularly, desirable derivatives can be obtained from the phenols and cresols containing a substituent derived from olefines containing from 8 to 18 carbon atoms, such as diisobutylene, and other alkylenes as nonylene, decylene, undecylene and dodecylene, pentadecylene,,octadecylene and mixtures thereof; and may advantageously be the dimers and trimers obtained by polymerization of such low molecular weight olefines as propylene, butylene, amylene or mixtures thereof. However, the water-soluble polyalkylene oxide derivatives of other water-insoluble organic compounds containing at least 6 carbon atoms, and having an active hydrogen, may be employed in the compositions of the present invention. Thus, the

polyalkylene oxide derivatives, described "in U.S. Patent No. 1,970,578, of aliphatic organic hydroxy compounds, carboxy compounds and amino compounds, as well as phenolic'compounds, may be employed if desired, As

- hydrogenation of the fatty acids of glycerides present in animal or vegetable oils and waxes, such as coconut oil, castor oil and the like. There may also be used polyalkylene oxide derivatives of higher molecular weight amines, such as octyl amine, cetyl amine, oleyl amine, 'naphthyl amines, alkyl anilines, etc.; also the polyalkylene oxide derivatives of organic mercapto compoundspsuch as the products described in U.S. Patent 2,205,021, i.e., the polyalkylene oxide derivatives of such mercapto compounds as dodecyl mercaptan, oleyl mercaptan, cetyl mercaptan, decyl mercaptan and thiophenols, thionaphthols, benzo-mercaptan, etc.; also the polyalkylene oxide derivatives, such as those described in U.S. Patent No. 2,085,706, of carboxylic acid amides, and of sulfonamides of the type described in U.S. Patent No. 2,002,613, or the polyalkylene oxide derivatives, described in U.S. Patent No. 2,266,141, of sulfonic acids may be employed, if desired.

It has been found that, in aqueous solutions of the novel nonionic surface active-iodine compositions of the present invention,'like other known aqueous products containing iodine; i.e., Lugols solution, only a portion of the total iodine incorporated in the composition is present in the form of available iodine, i.e., the form which can be titrated with sodium thiosulfate, using starch as an indicator. The total iodine in the product can be determined by combustion methods, such as that formulated by Hallett in Scotts Standard Methods of Chemical Analysis. The nonionic surface active agent employed in producing the products of the present invention, also, have the property of rendering the iodine soluble in aqueoussolutions. This property was quite unexpected, since it was previously considered necessary to include soluble iodide salts, such as KI, in iodine compositions which were to be used in aqueous medium, such as the well known Lugols solution of iodine. It also has been found that, under conditions of use in an aqueous medium, the novel nonionic surface active-agents iodine compositions of the present invention appear to release iodine slowly in solution, since the iodine is more slowly depleted from the solution when successive increments of soil are'added thereto, than it is depleted from other aqueous forms of iodine, such as Lugols solution. This slow depletion of iodine from aqueous solutions of the novel products of the present invention is readily demonstrated by capacity tests, for germicidal actvity described by Shelanski and Cantor, in Soap and Sanitary Chemicals," for February 1951; and described in Available Chlorine Germicidal Equivalent Concentration, First Action, Official Method of Analysis, Association Official Agricultural Chemists, 1955, 8th edition, pp. 87-93. In such capacity tests, the nonionic surface active agentsiodine compositions of the present invention are'consider ably more effective than aqueous alcohol-iodine solut'ions (tinctures), or aqueous KI iodine solutions (Lugols), when all are diluted to contain the same concentration of available iodine; and, at a given concentration of available iodine, the novel products of the present invention have been found to kill a greater number of increments of bacteria in soil, than do the prior art forms of iodine, in these same tests.

:Inorder to more fully illustrate the present invention,

EXAMPLE II A series of water-soluble nonionic surface active agentsiodine compositions were prepared by adding varying amounts of iodine crystals to the watersoluble nonionic surface active agent obtained by the condensation of nonyl phenol with 8 to 10 moles of ethylene oxide.- The amount of this nonionic surface active agent, with the amount of iodine added thereto, are shown in Table I, below. These compositions were prepared by merely adding a weighed amount of the iodine crystals to a weighed amount of the nonionic surface active agent, and stirring until solution was complete. The products were then analyzed, the total iodine being determined by the combustion method, above-described, and available iodine by titration with sodium thiosulfate, using the starch as an indicator, or by potentiometric titration with sodium thiosulfate. The products were then tested in the usual FDA phenol coefiicient test, using Micrococcus pyogenes var. aureus 209, as the test organism, at 20 C. The phenol coefiicient so determined, based on available iodine, is given in Table I, below. Samples of the products were stored in glass-stoppered bottles, at room temperature, and were analyzed at the end of six weeks, and 12 weeks, for both total iodine and available iodine, described above. The results of these analyses are also given in Table I, below:

soluble in water. The specific nonionic surface active agents. employed in preparing these compounds, were a. Nonylphenol condensation with 15 oxide 17. Nonylphenol condensation with molecular proportions of ethylene oxide c. Nonylphenol condensation with molecular proportions of ethylene oxide d. Nonylphenol condensation with molecular proportions of ethylene oxide What is claimed is:

1. A germicidal detergent composition comprising a mixture of a liquid water-soluble, nonionic detergent of the formula moles of ethylene wherein R represents the residue of a water-insoluble organic compound containing at least 6 carbon atoms and having an active hydrogen, and n represents an integer of from 6 to 50, and a germicidally efiective amount of elemental iodine.

2. A germicidal detergent composition comprising a mixture of a liquid water-soluble, nonionic detergent of wherein R represents the residue of a compound selected from the group consisting of alkyl substituted phenols and alkyl substituted cresols having at least one and at Table] Analysis Analysis After Storage in Glass-Stoppered Bottles at Room Temperature Phenol Amt. of Amt. of Coefiiclent Sample N onlonlc Used Iodine Nonlonlc used in 6 weeks 12 Weeks No. Used, g. Used, g. Percent Percent Available Tot. Avall- Iodine Iodine able Percent Percent Percent Percent Iodine Tot Avatl- Total Available able 1 Nonylphenol 8-10 0.25 99.75 0.25 0.06 (300 .30 0.06 0.27 0.01

moles ethylene oxide.

The foregoing products all were found to be etfective most two alkyl groups in which alkyl groups the total in germicidal capacity tests, and were equal or superior 5 number of alkyl carbon atoms is from 6 to 18, and n to Lugols iodine, when dilutions having the same concentration of available iodine were used.

EXAMPLE III It has been found that the amount of ethylene oxide condensed with the hydrophobic compound employed in the preparation of the particular nonionic used in preparing the compositions of the present invention, is not highly critical, so long as suflicient ethylene oxide is used, so that the resultant product is water-soluble. Thus, products containing 10% available iodine were prepared by adding iodine crystals to nonionic surface active agents obtained by condensing nonylphenol with varying molar ratios of ethylene oxide, and stirring until solution was complete, suflicient' iodine being added so that, on analysis, the amount of available iodine in the product was 10%. All products were found to be effective germicides in capacity tests, being equal or superior, in these tests, to Lugols iodine, on the basis of available iodine content; and, in all products, the iodine was found to be represents an integer of from 6 to 50, effective amount of elemental iodine.

3. A germicidal detergent composition comprising a mixture of a liquid water-soluble, nonionic detergent of the formula CnHre wherein n is a number within the range of 8 to 9, and a germicidally effective amount of elemental iodine.

and a germicidally (References on following page) "OTHER -REFERENCES Chemical Industries, Mnrch 1943, pp. 32 6- 3 2 8," ar tici'e by Goldsmith, entitled Non-ionic Surface Active Agents.

m reien gs cuaep inflie jpa fefit UNITED STATES PATENTS "2,13,47 t' d rfi t 1 .3,1"

f if? 312 r Chem1cal Week, Dec. 22, 1951, pp. 19 and 20.

i Proceeding of the Chemical Specialties Manufacturing 2,599,140 Taub June 3, 1952 9 5 6 2,743,208 Marcuse et a1. Apr. 24, 1956 December 19

Claims (1)

1. A GERMICIDAL DETERGENT COMPOSITION COMPRISING A MIXTURE OF A LIQUID WATER-SOLUBLE, NONIONIC DETERGENT OF THE FORMULA