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Publication numberUS3281365 A
Publication typeGrant
Publication dateOct 25, 1966
Filing dateDec 23, 1963
Priority dateDec 23, 1963
Publication numberUS 3281365 A, US 3281365A, US-A-3281365, US3281365 A, US3281365A
InventorsKurt Moedritzer
Original AssigneeMonsanto Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Antiseptic detergent compositions
US 3281365 A
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Description  (OCR text may contain errors)

United States Patent 3,281,365 ANTISEPTIC DETERGENT COMPOSITIONS Kurt Moedritzer, Webster Groves, Mo., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Dec. 23, 1963, Ser. No. 332,945 11 Claims. (Cl. 252-107) This invention relates to new and novel detergent compositions and more particularly to detergent compositions containing a bacteriostatic agent.

Detergents of themselves are not effective in preventing or arresting the growth or action of microorganisms such as the Staphylococci, i.e., Staphylococcus aureous, either by inhibiting their activity or by destroying them. Thus, when such action is desired bacteriostatic agents must be incorporated into the detergent composition to fulfill this function. However, none of the known bacteriostatic agents which are efiective in the presence of detergent compositions aid in the cleansing action and, in fact, some are deleterious to such action. As can be appreciated, therefore, a bacteriostatic agent which also exhibits surface active properties and thereby aids the detergent in the cleansing action would represent an advancement in this art.

It is, therefore, an object of this invention to provide improved antiseptic detergent compositions.

It is a further object of this invention to provide detergent compositions having incorporated therein a bacteriostatic agent which exhibits surface active properties.

Other objects will become apparent from a reading of the following detailed description and the claims appended hereto.

It has been found that quaternary phosphonium halides of the following formula wherein R is an aliphatic group containing 6 or more carbon atoms; R R and R are members selected from the group consisting of aliphatic groups, aryl groups, alkaryl groups, aralkyl groups and alicyclic groups of from 1 to 12 carbon atoms; and X is a member selected from the group consisting of chlorine, bromine and iodine ions, unexpectedly exhibit bacteriostatic properties as well as surface active properties as will be more fully discussed hereinafter.

In the foregoing general Formula 1 wherein R represents an aliphatic group containing 6 or more carbon,- atoms, it is preferred that the group contain not over about 24 carbon atoms and the group may be a straight chain structure or branched chain structure and may be a saturated group as well as an unsaturated group containing both double and triple bonds, although it is preferred that the group be either an alkyl group or an ethylenically unsaturated group with the group containing from about 8 to 18 carbon atoms. When the symbols R R and R represent groups containing carbon chains, such as aliphatic groups, or groups containing alkyl moieties, i.e., alkaryl groups, such carbon chains may be a straight or branched chain structure. When the symbols R R and R represent groups containing unsaturated carbon chains, these chains may contain both double bonds and triple bonds as well as contain more than one of such bonds although it is preferred that when such symbols repreent unsaturated carbon chains they are mono-ethylenically unsaturated. When the symbols R R and R represent groups containing aromaticcarbon rings such as aryl groups or groups containing aryl moieties, i.e., alkaryl groups, such carbon rings are preferably monoor di-ring 3,281,365 Patented Oct. 25, 1966 groups with the mono-ring group being especially preferred. Although the groups represented by R R and R may be like or unlike, it is preferred that each of the groups contain not over about 8 carbon atoms. In addition, all of the groups represented by R R R and R may contain one or more of the following substituents: hydroxy groups, amino groups, amide groups, ester groups, sulfonyl groups, sulfo groups and nitro groups.

It has been found that the unsymmetrical tetraalkyl phosphonium halides of the following formula:

wherein R is an alkyl group containing from about 8 to 18 carbon atoms; R R and R are lower alkyl groups (l-S carbon atoms) and X is a member selected from the group consisting of bromine and chlorine ions, are particularly effective and especially preferred bacteriostatic agents as well as surface active agents.

Such compounds include:

( 1) trimethyl dodecyl phosphonium chloride (2) triethyl octylphosphonium bromide (3) trimethyl tetradecyl phosphonium chloride (4) tri-n-propyl octadecyl phosphonium bromide (5) tri-n-amyl decyl phosphonium chloride (6) triethyl decyl phosphonium chloride (7) trimethyl decyl phosphonium bromide (8) triethyl dodecyl phosphonium chloride (9) tri-isopropyl tetradecyl phosphonium bromide (10) tri-n-butyl decyl phosphonium chloride Examples of compounds other than of the preferred class described above which can be employed in :accordance with this invention include:

(1) triphenyl oleylphosphonium chloride (2) triethyl heptene-l phosphonium chloride (3) tricyclopentyl dodecylphosphonium chloride (4) tricyclohexyl tetradecylphosphonium bromide (5) tricyclohexyl decylphosphonium bromide (6) triphenyl hexadiene-l,5-phosphonium iodide (7) tribenzyl tetradecylphosphonium bromide 8) tribenzyl dodecylphosphonium chloride 9) tri-isoarnyl oleylphosphonium iodide (10) tri-isopropenyl decylphosphonium bromide (11) tri-p-tolyl heptene-l-phosphonium iodide (12) tri-p-tolyl decylphosphonium chloride (13) trixylyl tetradecylphosphonium bromide (14) tri-isobutenyl tetradecylphosphoniorn chloride (15) tripropenyl tetradecylphosphonium iodide (16) tri-n-butenyl decylphosphonium iodide (17) tri-isopropenyl hexadecylphosphonium iodide (18) triphenyl tetradecylphosphonium bromide (19) tribenzyl octylphosphonium chloride (20) tricyclohexyl octadecylphosphonium bromide The quaternary phosphonium halides of the present inventiou can be prepared by many various methods which include reacting in an inert atmosphere a triorgano phosphine with an aliphatic halide at temperatures of from about C. to about C. for a period of a few hours. The following is the reaction in equation form:

wherein the groups R R R R and X are the same as represented in the foregoing general Formula 1.

3 The following examples are presented to illustrate the invention, with parts by weight being used in the examples unles otherwie indicated.

Example 1 Example 2 In the same manner as indicated in Example 1, about 202 parts of tributyl phosphine and about 205 parts of dodccylchloride were reacted to yield tributyldodecyl phosphonium chloride, a viscous liquid.

Example 3 In the same manner as indicated in Example 1, about 202 parts of tributyl phosphine and about 273 parts of tetradecyl bromide were reacted to yield tributyl tetradecyl phophonium bromide, a waxy solid (M.P. 37 C.).

Example 4 In the same manneras indicated in Example 1, about 202 parts of tributyl phosphine and about 297 parts of hexadecyl bromide were reacted to yield tributyl hexadecyl phosphonium bromide, a waxy sOlid (M.P. 55 C.).

Example 5 In the same manner as indicated in Example 1, about 202 parts of tributyl phosphine and about 321 parts of octadecyl bromide were reacted to yield tributyl octadecyl phosphonium bromide, a waxy solid (M.P. 65 C.).

Example 6 In the same manner as indicated in Example 1, about 7.6 parts of trimethyl phosphine and about 25 parts of dodecyl bromide were reacted to yield trimethyl dodecyl phosphonium bromide, a white solid (M.P. 193 C.).

The term detergent includes soap, i.e., an alkali metal or amine salt of a fatty acid and/or fatty acid mixture, and synthetic detergents, particularly of the anionic, nonionic and amphoteric classes, including mixtures of these. The term antiseptic detergent composition refers to those detergent compositions which are satisfactory detergents and which are effective against Staphylococci.

The quaternary phosphonium halides of the present invention have been found to not only exhibit surfacetension-reducing properties in aqueous systems but also to exhibit effective bacteriostatic properties in such systems in the presence of detergent compositions. In general,

. quaternary phosphonium chlorides are normally liquids while the bromides are normally solids which permit versatile yet selective methods for formulating with detergent compositions. In addition, these bacteriostatic agents neither discolor the finished detergent composition nor are irritating to the skin. It is, of course, a distinct advantage of the bacteriostatic agents of the present invention that they additionally aid the detergent composition in its cleansing action by exhibiting surface active properties in aqueous systems.

The amounts of the quaternary phosphonium halides which are suitable for use in detergent compositions can vary depending upon the end use applications of the detergent composition, such as bar soap, hair shampoo and the like, and, in general, any amount which is antiseptically effective, i.e., effective against Staphylococcus, can be used with amounts below about 50% by weight of the detergent composition being usually acceptable and amounts from about .05% to 10% being preferred. Under some circumstances, some bacteriostatic activity can be found as low as .001% by weight of the detergent.

The invention is not to be limited to any particular method of preparing the detergent composition containing the bacteriostatic agent. The bacteriostatic agent can be mechanically mixed in, crutched in the detergent in the form of a slurry, or dissolved in a solution of the detergent. In addition, the bacteriostatic agent can be admixed with the detergent in any of the forms in which the detergent is manufactured in, as well as being added simultaneously or separately to an aqueous solution. In any event, the bacteriostatic agent is intended to be used with the detergent at the time of application as a cleansing agent.

The resulting antiseptic detergent composition, that is, the detergent and the bacteriostatic agent, of the present invention is generally effective when used in aqueous systems in conventional amounts such as is normally used with detergent compositions and which is generally about .2% concentraton or below.

In order to illustrate the surface active properties of the bacteriotsatic agents of the instant invention, the following table presents the surface tensions in dynes per centimeter of solutions at the indicated concentrations of these agents and distilled water at 25 C. as determined by the DuNuoy principle using the Fisher tensiomat. The surface tension of water is about 72.8 degrees/ cm. at this temperature. A reduction of the surface tension of water to about 30 dynes in .25% solution is considered excellent and if this reduction is maintained practically unchanged to a dilution as low as .05%, the material is considered an extremely active surface-tension-reducing agent.

As previously mentioned, the bacteriostatic agents of the present invention are effective in controlling bacterial growth in the presence of detergents such as an Ivory brand neutral high grade toilet soap which is a mixture of alkali metal salts of fatty acids analyzing about 46 weight percent oleic and linoleic acid, about 14 weight percent stearic acid, about 30 weight percent palmitic acid and about 10 weight percent of lower fatty acids (myristic, lauric, etc.), and when incorporated in such a soap ina weight ratio of one part to 50 parts soap are effective in low concentrations (from about 1 to p.p.m.) against an inoculum of a standard culture of Micrococcus pyogenes var. aureus (Staphylococcus aureus) of standard resistance in a Sabourards dextrose agar medium.

Comparable effectiveness can also be obtained when using other soaps such as a Lux brand solid neutral white toilet soap (a mixture of alkali metal salts of fatty acids whose fatty acid content analyzes about 45% oleic and linoleic, about 30% palmitic acid, about 10% stearic acid and about 15% lower fatty acids) as well as anionic, nonionic and amphoteric synthetic detergents. Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and lyophilic groups in their molecular structure and which ionize in an aqueous medium to give anions containing the lyophilic group. These compounds are usually the alkali metal salts of organic sulfonates or sulfates, particularly the sodium salts, such as alkyl aryl sulfonates (e.g. sodium dodecyl benzene sulfonate), sulfate of straight chain primary alcohols (e.g., sodium lauryl sulfate) and the like. Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain, usually polyoxyethylene, while the lyophilic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. For example purposes only, the polyethylene oxide condensates of alkyl phenols (e.g., condensation product formed from 1 mole nonyl phenol and moles ethylene oxide), the condensation products of aliphatic alcohols and ethylene oxide (e.g. condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide) are suitable nonionic surface active compounds in practicing the invention. Amphoteric surface active compounds can be broadly described as compounds which have both anionic and cationic groups in the same molecule. Examples of such compounds include sodium N-methyl taurate and sodium N-coco beta amino propionate.

While a detergent composition of the present invention need contain only a detergent and the quaternary phosphonium halide, it will be appreciated that the incorporation in the mixture of additional ingredients commonly used with cleansing agents, such as perfume, builders (e.g., sodium tripolyphosphate) anti-redeposition agents (e.g., carboxymethylcellulose), brightening agents (e.g., fluorescent dyes) and the like, is contemplated as being within the invention.

A further understanding of the detergent compositions described herein and processes for preparing the compositions will be obtained from the following specific examples which are intended to illustrate this invention, but not to limit the scope thereof, parts and percentages being by weight unless otherwise indicated.

Example 7 A detergent composition is prepared formulated as follows:

Parts The above composition is prepared by melting the soap in a suitable vessel at about 60 to 70 C. and adding the phosphonium bromide to the soap with agitation. The admixture is then poured into a suitable mold and allowed to solidify by cooling to room temperature (about 25 C).

Example 8 A liquid detergent composition is prepared formuulated as follows:

Additive: Parts Water 46.1 Sodium carboxymethyl cellulose (95% by weight) .5 Fluorescent dye .025 Disodium acid pyrophosphate 5.0

Nonionic organic active (nonyl phenol-ethylene oxide condensate) 10.0 Maleic anhydride-ethylene copolymer 1.0 Tetrapotassium pyrophosphate 20.0 Potassium hydroxide (45% by Weight) 6.7 Sodium silicate (Na O:SiO of 1:2) (44.1%

by weight) 10.0

Tributyl dodecyl phosphonium chloride 1.0

The above composition is prepared by heating the water to about 60 C. and thereafter adding the above additives to the water in a mixer in their above listed order, each additive being added and mixed under high shear agitation over a period of about 1 to about 7 minutes while ensuring that the temperature of the mix does not exceed about 80 C.

6 Example 9 An antiseptic shampoo composition is prepared formulated sa follows:

The above composition is prepared by melting the potassium stearate at about 60 to 70 C. and adding thereto the triethanol lauryl sulfate, methyl cellulose, propylene glycol and tributyl tetradecyl phosphonium cholride until the mixture is well mixed and blended and thereafter adding the water in such a manner as to prevent aeration.

What is claimed is:

1. An antiseptic detergent composition consisting essentially of a detergent selected from the class consisting of soap and organic synthetic detergents selected from the class consisting of non-soap anionic, nonionic and amphoteric surfactants and at least an antiseptically eitective amount of a quaternary phosphonium halide of the following formula wherein R is an aliphtic group containing from 6 to 24 carbon atoms; R R and R are members selected from the group consisting of aliphatic groups, aryl groups, alkaryl groups, aralkyl groups, and alicyclic groups of from 1 to 12 carbon atoms; and X is a member selected from the group consisting of chlormine, bromine, and iodine ions.

2. An antiseptic detergent composition according to claim 1, wherein said quaternary phosphonium halide is present in amounts below about 50% by weight of said compositions.

3. An antiseptic detergent composition according to claim 2, wherein said detergent is soap.

4. An antiseptic detergent composition according to claim 2, wherein said detergent is an organic synthetic detergent selected from the class consisting of non-soap anionic, nonionic and amphoteric surfactants.

5. An antiseptic detergent composition consisting essentially of a detergent selected from the class consisting of soap and organic synthetic detergents selected from the class consisting of non-soap anionic, nonionic and amphoteric surfactants and at least an antiseptically effective amount of an unsymmetrical tetra alkyl phosphonium halide of the following formula wherein R is an alkyl group containing from about 8 to 18 carbon atoms; R R and R are lower alkyl groups containing from 1 to 5 carbon atoms and X is a member selected from the group consisting of bromine and chlorine ions.

6. An antiseptic detergent composition according to claim 5, wherein said unsymmetrical quaternary alkyl phosphonium halide is present in amounts below about 50% by weight of said composition.

7. An antiseptic detergent composition according to claim 6, wherein said detergent is soap.

8. An antiseptic detergent composition according to claim 6, wherein said detergent is an organic synthetic detergent selected from the class consisting of non-soap anionic, nonionic and amphoteric surfactants.

9. An antiseptic detergent composition according to claim 5, wherein said unsymmetrical tetra alkyl phosphonium halide is present in amounts from about .05% to about 10% by weight of said composition.

10. An antiseptic detergent composition according to claim 9, wherein said unsymmetrical tetra alkyl phosphonium halide is tributyl dodecyl phosphonium chloride.

11. An antiseptic detergent composition according to claim 9, wherein said unsymmetrical tetra alkyl phosphonium halide is tributyl dodecyl phosphonium bromide.

References Cited by the Examiner UNITED STATES PATENTS 1,921,364 8/1933 Lommel et a1. 2,265,759 12/ 1941 Lawton et a1. 2,577,773 12/1951 Lambert 252107 XR 2,950,255 8/1960 Golf 252106 XR 3,141,821 7/1964 Compeau 252-106 XR LEON D. ROSDOL, Primary Examiner.

JULIUS GREENWALD, W. E. SCHULZ,

Assistant Examiners.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1921364 *May 17, 1929Aug 8, 1933Ig Farbenindustrie AgMedia for protecting furs, hairs, feathers, and animal textile products against the attack of animal and plant pests
US2265759 *Jun 6, 1939Dec 9, 1941Shell DevOil well treating fluid
US2577773 *Mar 26, 1947Dec 11, 1951Gen Aniline & Film CorpTernary detergent compositions
US2950255 *Jul 3, 1956Aug 23, 1960Gillette CoDetergent composition
US3141821 *Mar 17, 1959Jul 21, 1964Lehn & Fink Products CorpSynergistic combination of alkyl sulfonates, alkylaryl sulfonates and topical antibacterial agents for local antisepsis
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4188380 *Dec 20, 1976Feb 12, 1980Exxon Research & Engineering Co.Surface active quaternary higher dialkyl phosphonium salt biocides and intermediates
US4673509 *Aug 27, 1984Jun 16, 1987Albright & Wilson LimitedAdding phosphonium compound
US4874526 *May 26, 1988Oct 17, 1989Ciba-Geigy CorporationUsing phosphonium compound
US20120048809 *Aug 29, 2011Mar 1, 2012Riggs Jr Olen LChemicals for Oil Spill Cleanup
CN1111165C *May 15, 2000Jun 11, 2003南京化工大学Aldehyde acetal modified quaternary phosphate and its preparing method and use
EP0066544A1 *May 26, 1982Dec 8, 1982Ciba-Geigy AgWater treatment
EP0544619A1 *Nov 18, 1992Jun 2, 1993Ciba-Geigy AgProtection of non-aqueous systems with biocides
EP0549006A2 *Nov 9, 1992Jun 30, 1993Fmc Corporation (Uk) LimitedAmmonium and phosphonium salts and their use as biocides
EP0959122A1 *May 5, 1999Nov 24, 1999Bayer CorporationCleaning solution for optical surfaces of urine analyzers
Classifications
U.S. Classification510/390, 510/133, 510/382, 424/70.23, 987/110, 510/469, 514/139, 510/391, 510/319, 510/383
International ClassificationC11D1/38, C11D3/48, C07F9/00, C07F9/54, C11D1/60
Cooperative ClassificationC11D3/48, C11D1/60, C07F9/54
European ClassificationC11D3/48, C11D1/60, C07F9/54