US2746928A - Germicidal detergent compositions - Google Patents
Germicidal detergent compositions Download PDFInfo
- Publication number
- US2746928A US2746928A US295808A US29580852A US2746928A US 2746928 A US2746928 A US 2746928A US 295808 A US295808 A US 295808A US 29580852 A US29580852 A US 29580852A US 2746928 A US2746928 A US 2746928A
- Authority
- US
- United States
- Prior art keywords
- quaternary ammonium
- weight
- iodine
- long
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/12—Iodine, e.g. iodophors; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
Definitions
- This invention relates to a novel germicidal detergent composition. More particularly, the invention is concerned with a germicidal detergent composition comprising an organic anionic detergent and a quaternary ammonium germicide in chemical complex with a halogen.
- Anionic surface-active agents are commonly employed in detergent compositions. Although they are excellent cleansing agents, they have very little germicidal activity.
- Quaternary ammonium germicides are also well known. They have been increasingly employed as disinfectants for the sanitization of equipment in various industries such as the dairy industry, the food industry, laundries, etc. Although classified as surface-active agents, they are generally ineffective as detergents.
- anionic surface-active agents with quaternary ammonium germicides to obtain germicidal detergent compositions because the two re agents are not compatible.
- the cationic quaternary ammonium germieidein such a mixture reacts with the anionic surface-active agent with a resultant reduction in the germicidal activity of the quaternary ammonium germicide and a reduction in the detergency of the anionic.
- Halogens such as iodine, chlorine and bromine are also recognized as germicides or disinfectants. Their applications are limited because of their toxic vapors and tendency to stain skin and textiles. They are also highly corrosive to equipment and irritating to human tissue when employed in germicidal portions. When the halogens are combined with anionic detergents in an effort to prepare germicidal detergent compositions, the aforementioned undesirable features are carried over unabated rendering the compositions unsuitable for general use.
- a very effective germicidal detergent composition may be prepared comprising as its active ingredient a major proportion of an organic anionic detergent of the group consisting of alkali metal and alkaline earth metal salts of an organic sulfuric reaction product having in its molecular structure a higher alkyl radical of from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals and a minor proportion of a quater nary ammonium salt-halogen complex containing from about 0.01 to about 1.0 mols of physically-bound elemental halogen per mol of quaternary as determinable by thiosulfate titration, the cation radical of said quaternary ammonium salt being characterized by a molecular weight of at least 165 and said complex being substantially free of unbound halogen as demonstrated by a negative response to the starch-iodide paper test and, in the case of iodine, by a negative response to
- the germicidal detergent composition as described above States Extent is stable under normal conditions of use whether in dry or liquid form. No turbidity, precipitation or other indication of incompatibility of the organic anionic detergent and the cationic quaternary ammonium germicide is to be found in solutions containing the composition.
- compositions are excellent detergents and germicides. In normal use the compositions release no toxic vapors, nor do they cause permanent staining of skin and textiles.
- the organic anionic detergent of the composition according to this invention may be any of the well-recognized synthetic detergents of the sulfate and sulfonate types, as will be apparent from the many illustrations hereinafter disclosed. In the above concise description of the invention it has been termed the salt of an organic sulfuric reaction product.
- This latter expression is intended to signify that it includes the water-soluble alkali metal and alkaline earth salts of sulfuric esters, alkane sulfonic acids and alkyl aromatic sulfonic acids derived by the reaction of sulfuric acid, oleum or fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur trioxide complexes with pyridine of ethers, acetyl sulfuric acid, sulfuryl chloride, etc. with a high molecular weight organic compound characterized by a hydrophobic group such as the higher aliphatic alcohols, fatty acid monoglycerides, alkyl aromatic hydrocarbons, and the like, having an alkyl radical of from 8 to 18 carbon atoms.
- the quaternary ammonium salt-halogen complex in the composition of this invention may be any of the wellknown class of quaternary ammonium germicides to which a halogen such as iodine, bromine, or chlorine, or mixtures thereof, has been added to give a product containing an appreciable quantity of physically-bound elemental halogen as determinable by thiosulfate titration and which are substantially free of unbound elemental halogen as indicated, for example, by their failure to form halogen amines when contacted with ammonia vapors.
- a halogen such as iodine, bromine, or chlorine, or mixtures thereof
- the quaternary ammonium salt-halogen complexes are conveniently prepared by adding a halogen, such as iodine, in elemental form or in the form of an aqueous or alcoholic solution of tri-iodide to an aqueous solution of a quaternary ammonium germicide. Upon mixing, the halogen is taken up by the quaternary and held in a loosely-bound elemental form, whereby it is immobilized in a physical sense of the word.
- a halogen such as iodine
- the halogen may be added in any amounts up to the point where the quaternary ammonium salt is incapable of taking up additional halogen, as indicated by an appreciable halogen partial pressure, odor, discoloration of starch-iodide paper exposed to its vapors, or the formation of halogen amines when the addition product is tested with ammonia vapors.
- iodine which is a preferred halogen
- a starch color test may be employed to detect the presence of unbound iodine.
- radical X in the above formula is any salt-forming anionic radical.
- Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like.
- quaternary ammonium salts include those in which the molecule contains ether, amide or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N (laurylcolaminoformylmethyl) pyridinium chloride, etc.
- quaternary ammonium germicides are those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
- Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium salts, the N-(acylcolaminoformylmethyl)-pyridinium halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the alkyl radical contains from 8-18 carbon atoms.
- the halogen portion of the complex of this invention may be either iodine, bromine or chlorine, or mixtures thereof, with iodine being preferred. It may be added in various proportions to the quaternary ammonium germicides described above so long as excessive amounts in the form of free unbound halides in the final product are avoided.
- the amount of halogen that will combine with the particular quaternary ammonium germicide may vary according to the molecular weight of the quaternary, usually from about 0.01 to about 1.0 mols of halogen per mol of quaternary or, more desirably, from about 0.1 to about 0.7 mols of halogen per mol of quaternary are preferred.
- the chemical complexing of the halogens and the quaternary ammonium germicidies is conveniently carried out at ordinary room temperatures of about 70 F. In order to facilitate the reaction it is sometimes desirable to warm the reaction mixture slightly, e. g., to from about 100 F. to about 150 F.
- the organic anionic detergent of the composition of this invention may, as already mentioned, be any watersoluble alkali metal or alkaline earth salt of an organic sulfuric reaction product having in its molecular structure a higher molecular alkyl group of from 8-18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
- Specific examples of the salts include the sodium alkyl sulfates obtained from mixed higher alcohols produced by the reduction of coconut oil, palm kernel oil and other tropical nut oils, as well as the higher alcohols derived from sperm oil.
- Sodium salts of the sulfuric acid esters of higher fatty acid monoglycerides such as coconut oil fatty acid monoester of 1,2-dihydroxy propane-3 sulfuric acid ester and of sulfated higher fatty acid alkylol amides such as coconut oil fatty acid ethanol amide, are also suitable.
- Sodium salts of sulfated high molecular Weight unsaturated organic acids and esters thereof, such as sulfated oleic acid and sulfated butyl oleate may also be employed.
- water-soluble alkaline earth and alkali metal salts of sulfated high molecular weight olefins obtained by dehydration of fatty alcohols or decarboxylation of unsaturated fatty acids, such as oleic acid.
- Sodium salts of the sulfated ethers prepared from ethylene or propylene oxide and alkylated phenols or naphthols, such as the sodium salt of para-octyl phenoxy ethoxy ethyl sulfuric acid ester are also suitable for use in the composition according to this invention.
- Illustrative detergents of the sulfonate variety include the sodium salts of normal fatty alkane sulfonic acids prepared by sulfonation of kerosene and white oil frac tions of paraffin-base petroleums by the action of strong sulfonating agents such as sulfur trioxide or sulfuryl chloride.
- Alkali metal and alkaline earth salts of higher monofatty acid esters of 1,2-dihydroxypropane-3-sulfonic acid such as the sodium salt of coconut oil fatty acid monoester of l,Z-dihydroxypropane-B-sulfonic acid may be employed.
- Suitable sulfonates for use in the composition of this invention are the salts of higher fatty acid mono-esters of the lower molecular weight hydroxyalkyl sulfonic acids as, for example, the sodium salt of the oleic acid ester of isothionic acid and of higher acid amides of low molecular amino alkyl sulfonic acids such as the sodium salt of maleic acid amide of N-methyl taurine.
- Aklaline earth and alkali metal salts of the higher molecular weight alcohol esters of low molecular sulfocarboxylic acids such as the sodium salt of lauryl alcohol ester of sulfo-acetic acid may be employed as well as the alcohol esters of sulfo-dicarboxylic acids such as the sodium salt of di-octylsulfosuccinic acid which are also suitable for employment in the present composition.
- Watersoluble salts of the higher alkylated benzene sulfonic acids such as the sodium and potassium salts of dodecyl benzene and Keryl benzene sulfonic acids may also be employed as may the water-soluble alkaline earth and alkali metal salts of ethers of high molecular weight alcohols and low molecular hydroxysulfonic acids such as the sodium salt of monolauryl ether of l,Z-dihydroxypropane-3-sulfonic acid.
- composition of this invention may also contain foam stabilizers of the type illustrated by lauric isopropanol amide.
- the relative amounts of the organic anionic detergent and the quaternary ammonium salt-halogen complex may vary over a considerable range. Ordinarily, it is desirable that sufficient anionic detergent be employed to impart definite detergent properties to the composition when it is added to water for use. Sufi'icient quaternary ammonium germicide-halogen complex product should be employed to give the desired amount of germicidal activity to the aqueous solutions in which the compositions are used.
- the germicidal detergent compositions should contain from about to 99 parts by weight of the organic anionic detergent and from about 1 to about 5 parts by weight of the quaternary ammonium germicide-halogen complex.
- a foam stabilizer of the type mentioned above is employed to improve the sudsing properties of the foregoing compositions, usually from about 0.1 to 50, and more preferably from about 10 to 30, parts by weight of the foam stabilizer based on 100 parts by weight of the combined anionic detergent and quaternary-halogen complex should be used.
- the quaternary ammonium germicide-halogen complex product ordinarily contains from about 0.01 to about 1.0 mols of halogen per mol of quaternary ammonium germicide, and more desirably from about 0.1 to about 0.7.
- the quaternary ammonium germicide-halogen complex should contain from about 5 to about 25% by weight of halogen in physically-bound elemental form based on the quaternary, and preferably from about 10 to 20% by weight.
- the germicidal detergent composition of the present invention may be prepared in either dry or liquid form. Aqueous slurries of the compositions are adaptable to various conventional methods of drying, such as drum drying, spray drying, and the like. in its liquid form the germicidal detergent composition of the invention may contain water and various well-known organic so1- vents of the type commonly employed in liquid detergent compositions such as ethanol, isopropanol, etc.
- the germicidal detergent composition according to this invention may also contain various neutral and acid builders of inorganic and organic types which are well known in the detergent art. These builders include alkali metal and alkaline earth inorganic builders such as sodium sulfate, magnesium sulfate, sodium chloride, and the like. Acidic inorganic builders may be illustrated by sodium hydrogen phosphates, acid triphosphates, etc. Salts of sulfamic acid and of simple aromatic sulfonic acids such as benzene and naphthalene sulfonic acids may also be employed.
- alkali metal and alkaline earth inorganic builders such as sodium sulfate, magnesium sulfate, sodium chloride, and the like.
- Acidic inorganic builders may be illustrated by sodium hydrogen phosphates, acid triphosphates, etc. Salts of sulfamic acid and of simple aromatic sulfonic acids such as benzene and naphthalene sulfonic acids may also be employed.
- Example 1.94.6 grams of an approximately 50% by weight aqueous solution of dodecylbenzyl diethylethanol quaternary ammonium chloride was combined with 5.4 grams of iodine.
- the mixture was heated to a temperature of from about 120 to about 150 F. for a period of about minutes, while stirring continuously.
- the quaternary-iodine complex thus obtained had the following analysis:
- the iodine contained in the complex reacted with sodium thiosulfate, indicating that it was available as elemental iodine rather than being chemically substituted in the quaternary ammonium salt molecule.
- a negative starch color test in aqueous medium was obtained on the complex product, indicating that it was substantially free of unbound iodine.
- This germicidal detergent composition in dry form was found to be highly eifective as both a germicide and a detergent when tested in accordance with the procedures described below.
- Example 386 grams of 46.5% by weight aqueous solution of dodecylbenzyl trimethyl quaternary ammonium chloride were combined with 10 grams of iodine.
- the mixture was heated to a temperature of from about to F. for a period of about 20 minutes, while stirring continuously.
- the quaternary-iodine complex thus obtained had the following analysis:
- the iodine contained in the complex reacted with sodium triosulfate, indicating that it was available as elemental iodine, but the iodine of the complex did not give a positive starch color test.
- the dried germicidal detergent composition prepared TABLE I1 Bactericidal acitvity of germicidal detergent compositions at use concentrations Bacteria Count and Percent Reduction in Count 1 Quater- Per;
- Bacterial Culture consisting of mixture of Staphylococcus aureus. Escherichia c012, and Bacillus cereua.
- Example 2 in accordance with the procedure given in the above Example 2 was tested against a mixed culture of Staphylococcus aztrezls, Escherichia Joli, and Bacillus cereus, as previously described. Results of this test and a comparison with an ordinary dry detergent composition are set forth in the following table.
- Bacterial culture consisting of mixture oi Staphylococcus aureus, Escherichia colt, and Bacillus cereus.
- liquid blends of anionic detergent and quaternary-halogen complex product with foam stabilizer and solvent prepared as in Example 3 above were also tested against a mixed bacteria culture of Staphylococcus aureus, Es- 5 cherichia coli, and Bacillus cereus, as previously described. The results of these tests are given for an illustrative liquid blend in the following table.
- Composition B is a composition of Composition B:
- Bacterial Culture consisting of mixture of Staphylococcus aureus, Escherichia coli, and Bacillus cereus.
- the germicidal detergent composition of the present invention may be prepared in either dry or liquid form and, further, that various amounts of other materials commonly employed in detergent compositions such as foam number of plates washed and the resulting effect on the dishwater were noted.
- the foam height of the composition was determined according to the method of Ross & Miles published in the Oil & Soap Journal, vol. 18, pages 99-102 (May 1941). Table V which follows shows the results of the tests.
- test results tabulated above demonstrate the excellent detergent properties of the germicidal detergent compositions according to this invention.
- the compositions in addition to being highly germicidal, possess pronounced detergent properties equal to those of the germicidally inactive anionic detergent alone.
- a germicidal detergent composition consisting essentially of 70 to 99.5 parts by weight of an organic anionic detergent of the group consisting of water-soluble alkali metal salts of an organic sulfuric reaction product having in its molecular structure a higher molecular alkyl radical of from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals and 0.5 to 30 parts by Weight of a quaternary ammonium germicide halogen complex consisting of from about 0.01 to about 1.0 mo'ls of physicallybound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, longchain al
- a germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal salt of a higher aliphatic sulfuric acid ester having from 8 to 18 carbon atoms in the alkyl radical and about 0.5 to 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to about 0.7 mols of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benz
- a germicidal detergent-composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal salt of ahigher aliphatic sulfuric acid ester having from about 8 to 18 carbon atoms in the alkyl radical, from about 0.5 to 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of longchain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trirnethyl quaternary ammonium halides, long-
- a germicidal detergent composition consisting essentially of about to 99.5 parts by weight of an alkali metal alkyl aryl sulfonate having from 8 to 18 carbon atoms in the alkyl radical thereof and from about 0.5 to
- quaternary ammonium germicide and iodine complex consisting of from about 0.1 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative starch color test in a
- a germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal alkyl aryl sulfonate having from 8 to 18 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzy
- a germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-
- a germicidal detergent composition consisting essentially of about 70 to about 99.5 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.1 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl
- a germicidal detergent composition consisting essentially of about 95 to about 99 parts by weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl trimethyl quaternary ammonium chloride containing about by weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to '30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfate and the iodine and dodecyl benzyl trimethyl quaternary ammonium chloride complex.
- a germicidal detergent composition consisting essentially of about 95 to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl trimethyl quaternary ammonium chloride containing about 10% by Weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by Weight of the combined sulfonate and the iodine and dodecyl benzyl trimethyl quaternary ammonium chloride complex
- a germicidal detergent composition consisting essentially of from about to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl dimethyl benzyl quaternary ammonium chloride containing about 10% by Weight of physically-bound iodine in elemental form based on the dodecyl benzyl dimethyl quaternary ammonium chloride which is determinable by thiosulfate titration, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfonate and the iodine and dodecyl benzyl dimethyl benzyl qua
- a germicidal detergent composition consisting essentially of from about 95 to about 99 parts by Weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl group, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physicallybound iodine in elemental form based on the dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfate and the iodine and dodecyl benzyl diethyl
- a germicidal detergent composition consisting essentially of from about 95 to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl diethyl ethanol quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfonate and the iodine and dodecyl benzyl dieth
- a liquid germicidal detergent composition consisting essentially of about 45% by weight of sodium lauryl sulfate, about 1% by weight of dodecyl benzyl diethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl di-eihyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 26% by weight of ethanol and about 16% by weight of water.
- a liquid germicidal detergent composition consisting essentially of about 45% by weight of sodium dodecyl benzene sulfonate, about 1% by weight of dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 26% by weight of ethanol and about 16% by Weight of water.
- a liquid germicidal detergent composition consisting essentially of about 45% by Weight of sodium dodecyl benzene sulfonate, about 1% by weight of dodecyl benzyl trimethyl quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 28% by weight of isopropanol, and about 14% by weight of water.
- a dry germicidal detergent composition consisting essentially of about 38% by weight of sodium dodecyl benzene sulfonate, about 6% by weight of dodecyl benzyl diethyl ethanol quaternary ammonium chloride containing about 10% by weight of physically-bound iodine in elemental formed based on the dodecyl benzyl diethyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium and about 56% by weight of sodium sulfate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Agronomy & Crop Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Description
GERMICIDAL DETERGENT COMPOSITIONS John L. Darragh, Alamo, and Gordon B. Johnson, Berkeley, Califi, assignors to California Research CQK'EFGBQ tion, San Francisco, Calif., a corporation of Delaware No Drawing. Application June 26, 1952, Serial No. 295,808
16 Claims. or. 252-106) This invention relates to a novel germicidal detergent composition. More particularly, the invention is concerned with a germicidal detergent composition comprising an organic anionic detergent and a quaternary ammonium germicide in chemical complex with a halogen.
Anionic surface-active agents are commonly employed in detergent compositions. Although they are excellent cleansing agents, they have very little germicidal activity.
Quaternary ammonium germicides are also well known. They have been increasingly employed as disinfectants for the sanitization of equipment in various industries such as the dairy industry, the food industry, laundries, etc. Although classified as surface-active agents, they are generally ineffective as detergents.
It has not been possible to mix anionic surface-active agents with quaternary ammonium germicides to obtain germicidal detergent compositions because the two re agents are not compatible. The cationic quaternary ammonium germieidein such a mixture reacts with the anionic surface-active agent with a resultant reduction in the germicidal activity of the quaternary ammonium germicide and a reduction in the detergency of the anionic.
Halogens such as iodine, chlorine and bromine are also recognized as germicides or disinfectants. Their applications are limited because of their toxic vapors and tendency to stain skin and textiles. They are also highly corrosive to equipment and irritating to human tissue when employed in germicidal portions. When the halogens are combined with anionic detergents in an effort to prepare germicidal detergent compositions, the aforementioned undesirable features are carried over unabated rendering the compositions unsuitable for general use.
It has now been found that a very effective germicidal detergent composition may be prepared comprising as its active ingredient a major proportion of an organic anionic detergent of the group consisting of alkali metal and alkaline earth metal salts of an organic sulfuric reaction product having in its molecular structure a higher alkyl radical of from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals and a minor proportion of a quater nary ammonium salt-halogen complex containing from about 0.01 to about 1.0 mols of physically-bound elemental halogen per mol of quaternary as determinable by thiosulfate titration, the cation radical of said quaternary ammonium salt being characterized by a molecular weight of at least 165 and said complex being substantially free of unbound halogen as demonstrated by a negative response to the starch-iodide paper test and, in the case of iodine, by a negative response to the starch test. Preparation of suitable starch solution for such a test is noted at pages 70 and 71 of the book A System of Chemical Analysis for the Common Elements by Mr. E. H, Swift, published 1939 by Prentice-Hall, Inc. The absence of unbound halogen in the complex is demonstrated also by its failure to form halogen amines when exposed to ammonia vapors.
The germicidal detergent composition as described above States Extent is stable under normal conditions of use whether in dry or liquid form. No turbidity, precipitation or other indication of incompatibility of the organic anionic detergent and the cationic quaternary ammonium germicide is to be found in solutions containing the composition.
The compositions are excellent detergents and germicides. In normal use the compositions release no toxic vapors, nor do they cause permanent staining of skin and textiles.
The organic anionic detergent of the composition according to this invention may be any of the well-recognized synthetic detergents of the sulfate and sulfonate types, as will be apparent from the many illustrations hereinafter disclosed. In the above concise description of the invention it has been termed the salt of an organic sulfuric reaction product. This latter expression is intended to signify that it includes the water-soluble alkali metal and alkaline earth salts of sulfuric esters, alkane sulfonic acids and alkyl aromatic sulfonic acids derived by the reaction of sulfuric acid, oleum or fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid, sulfur trioxide complexes with pyridine of ethers, acetyl sulfuric acid, sulfuryl chloride, etc. with a high molecular weight organic compound characterized by a hydrophobic group such as the higher aliphatic alcohols, fatty acid monoglycerides, alkyl aromatic hydrocarbons, and the like, having an alkyl radical of from 8 to 18 carbon atoms.
The quaternary ammonium salt-halogen complex in the composition of this invention may be any of the wellknown class of quaternary ammonium germicides to which a halogen such as iodine, bromine, or chlorine, or mixtures thereof, has been added to give a product containing an appreciable quantity of physically-bound elemental halogen as determinable by thiosulfate titration and which are substantially free of unbound elemental halogen as indicated, for example, by their failure to form halogen amines when contacted with ammonia vapors. These complexes are fully described in the copending U. S. patent application Serial No. 254,815 of John L. Darragh and Ralph House, now U. S. Patent No. 2,679,533 issued May 25, 1954. The quaternary ammonium salt-halogen complexes are conveniently prepared by adding a halogen, such as iodine, in elemental form or in the form of an aqueous or alcoholic solution of tri-iodide to an aqueous solution of a quaternary ammonium germicide. Upon mixing, the halogen is taken up by the quaternary and held in a loosely-bound elemental form, whereby it is immobilized in a physical sense of the word. The halogen may be added in any amounts up to the point where the quaternary ammonium salt is incapable of taking up additional halogen, as indicated by an appreciable halogen partial pressure, odor, discoloration of starch-iodide paper exposed to its vapors, or the formation of halogen amines when the addition product is tested with ammonia vapors. In the case of iodine, which is a preferred halogen, a starch color test may be employed to detect the presence of unbound iodine.
The quaternary ammonium salt may be any of the well-known class of quaternary ammonium germicides characterized by the formula:
xi R1 R phenoxy alkyl, aryl alkyl, etc. in nature. The remaining radicals on the nitrogen atom other than the hydrophobic radicals are substituents of hydrocarbon structure usually containing a total of no more than 12 carbon atoms. The radical X in the above formula is any salt-forming anionic radical.
Suitable quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains ether, amide or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N (laurylcolaminoformylmethyl) pyridinium chloride, etc. Other very effective types of quaternary ammonium germicides are those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
Preferred quaternary ammonium germicides of the above general types are the long-chain alkyl dimethylbenzyl quaternary ammonium salts, the alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium salts, the N-(acylcolaminoformylmethyl)-pyridinium halides, the long-chain alkyl trimethyl ammonium halides, the long-chain alkyl benzyl trimethyl ammonium halides, the long-chain alkyl benzyl dimethyl benzyl ammonium halides, and the long-chain alkyl benzyl diethyl ethanol ammonium halides in which the alkyl radical contains from 8-18 carbon atoms.
As mentioned before, the halogen portion of the complex of this invention may be either iodine, bromine or chlorine, or mixtures thereof, with iodine being preferred. It may be added in various proportions to the quaternary ammonium germicides described above so long as excessive amounts in the form of free unbound halides in the final product are avoided. Although the amount of halogen that will combine with the particular quaternary ammonium germicide may vary according to the molecular weight of the quaternary, usually from about 0.01 to about 1.0 mols of halogen per mol of quaternary or, more desirably, from about 0.1 to about 0.7 mols of halogen per mol of quaternary are preferred.
The chemical complexing of the halogens and the quaternary ammonium germicidies is conveniently carried out at ordinary room temperatures of about 70 F. In order to facilitate the reaction it is sometimes desirable to warm the reaction mixture slightly, e. g., to from about 100 F. to about 150 F.
The organic anionic detergent of the composition of this invention may, as already mentioned, be any watersoluble alkali metal or alkaline earth salt of an organic sulfuric reaction product having in its molecular structure a higher molecular alkyl group of from 8-18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Specific examples of the salts include the sodium alkyl sulfates obtained from mixed higher alcohols produced by the reduction of coconut oil, palm kernel oil and other tropical nut oils, as well as the higher alcohols derived from sperm oil. Sodium salts of the sulfuric acid esters of higher fatty acid monoglycerides such as coconut oil fatty acid monoester of 1,2-dihydroxy propane-3 sulfuric acid ester and of sulfated higher fatty acid alkylol amides such as coconut oil fatty acid ethanol amide, are also suitable. Sodium salts of sulfated high molecular Weight unsaturated organic acids and esters thereof, such as sulfated oleic acid and sulfated butyl oleate may also be employed. Also suitable are the water-soluble alkaline earth and alkali metal salts of sulfated high molecular weight olefins obtained by dehydration of fatty alcohols or decarboxylation of unsaturated fatty acids, such as oleic acid. Sodium salts of the sulfated ethers prepared from ethylene or propylene oxide and alkylated phenols or naphthols, such as the sodium salt of para-octyl phenoxy ethoxy ethyl sulfuric acid ester are also suitable for use in the composition according to this invention.
Illustrative detergents of the sulfonate variety include the sodium salts of normal fatty alkane sulfonic acids prepared by sulfonation of kerosene and white oil frac tions of paraffin-base petroleums by the action of strong sulfonating agents such as sulfur trioxide or sulfuryl chloride. Alkali metal and alkaline earth salts of higher monofatty acid esters of 1,2-dihydroxypropane-3-sulfonic acid such as the sodium salt of coconut oil fatty acid monoester of l,Z-dihydroxypropane-B-sulfonic acid may be employed. Also illustrative of suitable sulfonates for use in the composition of this invention are the salts of higher fatty acid mono-esters of the lower molecular weight hydroxyalkyl sulfonic acids as, for example, the sodium salt of the oleic acid ester of isothionic acid and of higher acid amides of low molecular amino alkyl sulfonic acids such as the sodium salt of maleic acid amide of N-methyl taurine. Aklaline earth and alkali metal salts of the higher molecular weight alcohol esters of low molecular sulfocarboxylic acids such as the sodium salt of lauryl alcohol ester of sulfo-acetic acid may be employed as well as the alcohol esters of sulfo-dicarboxylic acids such as the sodium salt of di-octylsulfosuccinic acid which are also suitable for employment in the present composition. Watersoluble salts of the higher alkylated benzene sulfonic acids such as the sodium and potassium salts of dodecyl benzene and Keryl benzene sulfonic acids may also be employed as may the water-soluble alkaline earth and alkali metal salts of ethers of high molecular weight alcohols and low molecular hydroxysulfonic acids such as the sodium salt of monolauryl ether of l,Z-dihydroxypropane-3-sulfonic acid.
In addition to the organic anionic detergent, the composition of this invention may also contain foam stabilizers of the type illustrated by lauric isopropanol amide.
The relative amounts of the organic anionic detergent and the quaternary ammonium salt-halogen complex may vary over a considerable range. Ordinarily, it is desirable that sufficient anionic detergent be employed to impart definite detergent properties to the composition when it is added to water for use. Sufi'icient quaternary ammonium germicide-halogen complex product should be employed to give the desired amount of germicidal activity to the aqueous solutions in which the compositions are used.
Usually from about to 99.5 parts by weight of the organic anionic detergent and about 0.5 to 30 parts by Weight of the quaternary ammonium germicide-halogen complex will be found satisfactory. More preferably the germicidal detergent compositions should contain from about to 99 parts by weight of the organic anionic detergent and from about 1 to about 5 parts by weight of the quaternary ammonium germicide-halogen complex. When a foam stabilizer of the type mentioned above is employed to improve the sudsing properties of the foregoing compositions, usually from about 0.1 to 50, and more preferably from about 10 to 30, parts by weight of the foam stabilizer based on 100 parts by weight of the combined anionic detergent and quaternary-halogen complex should be used.
As already mentioned, the quaternary ammonium germicide-halogen complex product ordinarily contains from about 0.01 to about 1.0 mols of halogen per mol of quaternary ammonium germicide, and more desirably from about 0.1 to about 0.7. On a per cent by weight basis, the quaternary ammonium germicide-halogen complex should contain from about 5 to about 25% by weight of halogen in physically-bound elemental form based on the quaternary, and preferably from about 10 to 20% by weight.
TABLE I Immobilization of iodine as tested with starch as an external indicator Iodine Take-up Before Yielding Starch Test Compound Gms. I; per Mols Iqper gm. Commoi Compound pound Dodecyl benzyl trimethyl ammonium chloride 0. 40%). 47 0. (H). 7 Dodecyl benzyl dimethyl benzyl ammonium chloride 0. 393 0. 65 Cetyl pyridinium bromide (crystalline) 0. 09 0. 14 di-(dodecyl benzyD-dimethyl ammonium chloride 0. 24-0. 25 0. 580. 61 di-n-octylbenzyl-di-methyl ammonium chloride 0. 27 0.52 Dodecylphenyl trimethylamm um methosulfate 0. 29 0. 49 'Iribenzyl methylammonium methosuliate. 0. 25 0. 40 Dodecylbenzyltriethanolammonium chloride 0. 0440. 048 0. 079-0. 084 p-tertiary octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride t 0. 32-0. 38 0. 58-0. 68 Octadecyl dimethyl benzyl ammonium bromide i 0. 42 0. 59 Tetramcthyl ammonium chloride.-. Nil Nil Trimethyl phenyl ammonium chloride N i] Nil Nitrobenzyltrimethyl ammonium chloride" Nil Nil n-octylbenzyl thiuronium chloride Nil Nil It will be noted from the results tabulated above that it is the quaternary ammonium salts of a high molecular weight, usually having a molecular weight of at least 165 in the cation radical, which are preferred for taking up the halogen. These high molecular weight quaternary ammonium salts are generally referred to as quaternary ammonium germicides and it is in that sense that the term has been employed in discussing the quaternary ammonium germicide-halogen complex products of the present composition.
The germicidal detergent composition of the present invention may be prepared in either dry or liquid form. Aqueous slurries of the compositions are adaptable to various conventional methods of drying, such as drum drying, spray drying, and the like. in its liquid form the germicidal detergent composition of the invention may contain water and various well-known organic so1- vents of the type commonly employed in liquid detergent compositions such as ethanol, isopropanol, etc.
The germicidal detergent composition according to this invention may also contain various neutral and acid builders of inorganic and organic types which are well known in the detergent art. These builders include alkali metal and alkaline earth inorganic builders such as sodium sulfate, magnesium sulfate, sodium chloride, and the like. Acidic inorganic builders may be illustrated by sodium hydrogen phosphates, acid triphosphates, etc. Salts of sulfamic acid and of simple aromatic sulfonic acids such as benzene and naphthalene sulfonic acids may also be employed.
Although it is believed that the nature of the germicidal detergent composition of this invention will be clearly understood from the foregoing descriptions, the following examples are offered as additional illustrations. Unless otherwise specified, the proportions given are on a weight basis.
Example 1.94.6 grams of an approximately 50% by weight aqueous solution of dodecylbenzyl diethylethanol quaternary ammonium chloride was combined with 5.4 grams of iodine. The mixture was heated to a temperature of from about 120 to about 150 F. for a period of about minutes, while stirring continuously. The quaternary-iodine complex thus obtained had the following analysis:
Percent Dodecylbenzyl diethylethanol quaternary ammonium chloride 46.3 Iodine 5.1 Water 48.6
The iodine contained in the complex reacted with sodium thiosulfate, indicating that it was available as elemental iodine rather than being chemically substituted in the quaternary ammonium salt molecule. A negative starch color test in aqueous medium was obtained on the complex product, indicating that it was substantially free of unbound iodine.
16.2 grams of the dodecylbenzyl diethylethanol quaternary ammonium chloride-iodine complex prepared above were mixed with 96.5 grams of a detergent composition comprising 51.8% of dodecylbenzene sodium sulfonate, 32.6% isopropanol and 15.6% water. The resulting mixture possessed the following analysis:
Per cent Dodecylbenzyl diethylethanol quaternary ammonium chloride-iodine 8.0 Dodecylbenzene sodium sulfonate 47.8 Isopropanol 29.8 Water 14.4
to give the following composition:
Per cent Dodecyl benzene sodium sulfonate 37.5 Dodecylbenzyl diethylethanol quaternary ammonium chloride-iodine complex 6.3 Sodium sulfate 56.2
This germicidal detergent composition in dry form was found to be highly eifective as both a germicide and a detergent when tested in accordance with the procedures described below.
Example 3.86 grams of 46.5% by weight aqueous solution of dodecylbenzyl trimethyl quaternary ammonium chloride were combined with 10 grams of iodine. The mixture was heated to a temperature of from about to F. for a period of about 20 minutes, while stirring continuously. The quaternary-iodine complex thus obtained had the following analysis:
Per cent Dodecylbenzyl trimethyl quaternary ammonium chloride 41.6 Iodine 10.4 Water 48.0
The iodine contained in the complex reacted with sodium triosulfate, indicating that it was available as elemental iodine, but the iodine of the complex did not give a positive starch color test.
4.2 grams of the dodecylbenzyl trimethyl quaternary ammonium chloride-iodine complex were mixed with 200 grams of a detergent composition comprising 45.5% of dodecylbenzene sodium sulfonate, 12.1% lauric isopropanol amide, 28.6% isopropanol, and 13.8% water. The resulting mixture possessed the following analysis:
7 Per cent Dodeeylbenzyl trimethyl quaternary ammonium This composition was found to possess a high degree of germicidal activity and excellent detergent properties.
' From the tabulated results it is readily apparent that when a typical quaternary ammonium germicide such as dodecyl benzyl trimethyl ammonium chloride is mixed with a typical anionic detergent such as dodecyl benzene sodium sulfonate, the bactericidal activity of the quaternary is markedly decreased. On the other hand, when a quaternary ammonium germicide-halogen complex product is employed with the anionic detergent in accordance with the principle of this invention, a very high In illustration of the effectiveness of the germicidal 10 bactericiqal is found The bactericidifl activity detergent composition according to the invention, various the amomc detergent and 99 19 ammomum germ representative compositions were tested against samples lclde'haiqgen comPositlon is fully as good of sterile water artificially inoculated with a mixed culc?mposltlons Cqntammg amomc f' g and free ture of Staphylococcus aureus, Escherichia coli, and Ba- A mentions? before amomc letefgem and cillus Cereus, which are all commonly known bacteria 10 free iodlne compositions are entirely unsatisfactory, not
for the testing of germicidal agents. The tests were carbecause of lack of germlcldzfl actlvlty, but, rather, ried out at various concentrations of organic anionic de- Cause of their toxic Vapors, 1111511 tendency to Stain Skin d tergent and quaternary ammonium germicide-halogen textiles, and their corrosive action on equipment and hucomplex and the decrease in number of bacteria was ohman tissue. served at different times. 20 The dried germicidal detergent composition prepared TABLE I1 Bactericidal acitvity of germicidal detergent compositions at use concentrations Bacteria Count and Percent Reduction in Count 1 Quater- Per;
narv cen p. p. m. Anionic r minutes minutes minutes minutes minutes Quaternary Halo Quaterg Deter- B gen nary 10 me gent monn. (Mame) Deter Per For For P P Ratio gent Count cent Count cent Count cent Count cent Count cent Red. Red. Red. Red. Red.
None (Control) 41 1o 52X10 49x10 ssxio 49 10 Dodecyl Benzyl trimethyl ammonium chloride 200 0 100 1 100 0 100 0 100 Do 200 0.50 253x10 40.2 78 10 85.0 53x10 89.2 57x10 89.8 66 10 36.8 Do 200 1.0 34x10 28.7 517x10 83.3 73 1o= 84.1 53x10 91.6 60x10 87.3 None,(Control) 7X10 52 l0 19x10 59x10 49x10 Dodecyl benzyl trimethyl ammonium chloride-iodine com- 7 90/10 200 22 0. 0 0 100 100 100 100 100 90/10 200 22 0.05 57x10 99.988 36 10 99.993 30x10 99.994 39x10: 99993 22x10 99.996 90/10 200 22 1.0 372 99.999 400 99. 999 221 99- 999 100 10 99.999 N 41x10 43X10 42x10 44x10 47 10 Dodecyl benzyl diethyl ethanol quaternary ammonium chlorideiodine complex 90/10 200 22 0. 0 100 100 100 0 100 100 Do 90/10 200 22 0.05 62 (10 99.849 47X10 99.893 26X10 99.938 12 10 99.973 13x10 99.979 D0 90/10 200 22 i) 1.0 13X10 99.683 X10 99.814 21X10 99.950 l6 10 99.964 18 10 99.962 None, (Oontrol) 41X10 43x10 42X10 44X10 47 10 Dodecyl benzyl d1- methyl benzyl quaternary ammonium chloride-iodine complex- /10 200 22 0.0 0 0 100 0 100 0 100 0 100 Do 90/10 2 22 0.05 93X10 99. 774 87 10 99. 978 97 10 99. 759 83 10 99.811 68x10 99.855 None (Control), v 49x10 46X10 47X10 17)(10 12x10 Oetadeeyl dimethylhenzyl ammonium bromide 200 0.5 22 (10 55-1 19X10 58.6 17 (l0 03.8 14x10 70.2 72X10 82.9 Octadecyl dimetliiylbenzyl ammonium bromide-iodine complex 90/10 200 22 0.5 260 99.999 201 99.999 1 99.999 72 99.999 18 99.999 None (Control) 49x10 46x10 17x10 47 10 42x10 p-tert-octyl phenoxyethoxy ethyl dimethy l benzyl ammonium chloridt= 200 0.5 15X10 69.4 l2 10 73.9 18X10 61.7 11Xl0 70.6 9x10 78.6 p-tert-octyl phenoxyethoxy ethyl dtmethyl ammonium chlorideiodine comple:-; 90/10 200 22 0.5 5X10 99.990 400 99.999 800 99.998 700 99. 999 800 99.998 None (Control) 49X10 415x10 47x10 47x10 42X10 N-(acylcolaminoformylmethyD-pyridinmm chloride 200. 0.5 18X10 63.2 10x10 78.2 8X10 83.0 0X10 87.2 3X10 92.8 N-(aoyicolaminoformylmethyD-pyridinium chloride-iodine comv plex 90/10 200 22 0.5 19 10 99.961 9X10 99.980 50410 99938 61x10 99.987 800 99.993 None (Control) 49X10 46X10 47x10 47 10 42x10 Catylpyridinium bromidi 200 0.5 12x10 75.6 10 10 78.2 l0 10 78.8 7X10 85.1 8X10 81.0 Cetylpyridinium bromide-iodine complex 90/10 200 22 0.5 800 99.998 700 99.998 11 10 99. 998 600 99.999 400 99.999 None (Control) 41x10 43x10 42x10 14x19 47 10 1 d 22 0.0 500 99.999 70 99.999 0 100 0 100 0 100 22 0. 05 25x10 99.939 31 10 99.928 32X10 99.924 24X10 99.945 10X10 99.979 22 1.0 34x10 99. 917 39x10 99.909 40Xl0 99.905 28 (10 99. 930 14x10 99.970
1 Bacterial Culture consisting of mixture of Staphylococcus aureus. Escherichia c012, and Bacillus cereua.
B Dodecyl benzene sodium sulionate.
in accordance with the procedure given in the above Example 2 was tested against a mixed culture of Staphylococcus aztrezls, Escherichia Joli, and Bacillus cereus, as previously described. Results of this test and a comparison with an ordinary dry detergent composition are set forth in the following table.
TABLE III Bactericidal activity of dried detergent compositions at use concentrations Bacteria Count and Percent Reduction in Count 1 Concencompusition g, 5 Minutes 10 Minutes Minutes Minutes 60 Minutes ilr'eight, ercent Percent Percen Percent Percen Percent Count Red. Count Red. Count Count Count Control 44 10 48X10 42 10 46 10 43x10 Compotsiitiorli A}; d
o ecy enzene so rum sulfonate, 0, 075 47 10 +6. 9 42x10 12. 5 463x10 +9. 5 41 10 10. 9 46 10 +6. 9 Sodium sulfate, Composition B:
Dodecyl benzene sodium S s-11ltonatefi3t7.5% 2
e um Su 2 e, 56. D o d 6 Gym enzyl dfethyl 0. 08 9X10 99. 758 12 10 99. 750 4X10 99. 905 127 99. 972 188 99. 906
ethanol quaternary ammonium chloride-Iodine, 6.3%.
1 Bacterial culture consisting of mixture oi Staphylococcus aureus, Escherichia colt, and Bacillus cereus.
As a further demonstration of the utility of the germicidal detergent compositions according to this invention, liquid blends of anionic detergent and quaternary-halogen complex product with foam stabilizer and solvent prepared as in Example 3 above were also tested against a mixed bacteria culture of Staphylococcus aureus, Es- 5 cherichia coli, and Bacillus cereus, as previously described. The results of these tests are given for an illustrative liquid blend in the following table.
30 anionic detergent, dodecylbenzene sodium .sulfonate, with TABLE IV Bactericidal activity of liquid detergent compositions at use concentrations Bacteria Count and Percent Reduction in Count 1 Cotn cen re- Composition tion by 5 minutes 10 minutes 20 minutes 30 minutes 60 minutes 'geight, ercent Percent Percen Percen Percent Percent Count Red Count; Count Rem Count Count Red Control 47x10 51 10 51x10 49x10 54x10 Percent by Wt. iti it e n t T o eey enzene so iums ona e- Laurie isopr 0pm 01 amide 12 0. 00 310 99. 9 220 99.9 41 99. 9 86 99. 9 67 99. 9 Ethanol 26 Water 16 Dodecylbenzyl diethyl ethanol quaternary ammonium chloride Iodine 1.0
Composition B:
Sodium lauryl sulfate i. 45 Laurie isopropanol amide. 12 #32 0,1 22 10 95.4 5x10 99.0 2x10 99.6 16x10 99.1 4x10 99.9 Dodecylbenzyldiethyl ethanol qua ternary ammonium chloride 10- dine 1.0
1 Bacterial Culture consisting of mixture of Staphylococcus aureus, Escherichia coli, and Bacillus cereus.
it is apparent from the results tabulated above that the germicidal detergent composition of the present invention may be prepared in either dry or liquid form and, further, that various amounts of other materials commonly employed in detergent compositions such as foam number of plates washed and the resulting effect on the dishwater were noted. The foam height of the composition was determined according to the method of Ross & Miles published in the Oil & Soap Journal, vol. 18, pages 99-102 (May 1941). Table V which follows shows the results of the tests.
TABLE V Dishwashing Test, 15 gm. Lard Oil/Plate its Solution Water Number of Plates Fo ai Compound Percent 62% g? Temp" Foam Washed Test, k Foam percen D. ph 7 7 57 Height,
- Area Dept 95 50 mm. Imtlal Fmal percer'it in. Foaiii Foaih Foain Dodecylbenzene sodium sultonate 45. Laurie isopropanol amide 12. 1 O. 05 300 120 112 100 0. 4 13 119 Alcohol and water 42. 4
Dodecylbeuzene sodium sultonato 44. 5 Laurie isopropanol amide 11. 8 Dodecylbenzyl trimethyl quaternary am- 0. O6 300 121 114 100 0. 32 3 11 26 112 monium chloride-Iodine 1. 0 Alcohol and water 42. 7
The test results tabulated above demonstrate the excellent detergent properties of the germicidal detergent compositions according to this invention. The compositions in addition to being highly germicidal, possess pronounced detergent properties equal to those of the germicidally inactive anionic detergent alone.
We claim:
1. A germicidal detergent composition consisting essentially of 70 to 99.5 parts by weight of an organic anionic detergent of the group consisting of water-soluble alkali metal salts of an organic sulfuric reaction product having in its molecular structure a higher molecular alkyl radical of from 8 to 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals and 0.5 to 30 parts by Weight of a quaternary ammonium germicide halogen complex consisting of from about 0.01 to about 1.0 mo'ls of physicallybound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, longchain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound halogen as demonstrated by its failure to form halogen amines when exposed to ammonia vapors.
2. A germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal salt of a higher aliphatic sulfuric acid ester having from 8 to 18 carbon atoms in the alkyl radical and about 0.5 to 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to about 0.7 mols of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium.
3. A germicidal detergent-composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal salt of ahigher aliphatic sulfuric acid ester having from about 8 to 18 carbon atoms in the alkyl radical, from about 0.5 to 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of longchain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trirnethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium and about 0.1 to 50 parts by weight of a fatty acid lower alkanol amide, based on 100 parts by weight of the combined sulfuric acid ester salt and the quaternary ammonium germicideiodine complex.
4. A germicidal detergent composition consisting essentially of about to 99.5 parts by weight of an alkali metal alkyl aryl sulfonate having from 8 to 18 carbon atoms in the alkyl radical thereof and from about 0.5 to
about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.1 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium.
5. A germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal alkyl aryl sulfonate having from 8 to 18 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 0.1 to 50 parts by weight of a fatty acid lower alkanol amide based on 100 parts by weight of the combined sulfonate and quaternaryiodine complex.
6. A germicidal detergent composition consisting essentially of about 70 to 99.5 parts by weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.01 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 0.1 to 30 parts by weight of a fatty acid lower alkanol amide based on 100 parts by weight of the combined sulfate and the quaternary ammonium germicide and iodine complex.
7. A germicidal detergent composition consisting essentially of about 70 to about 99.5 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 0.5 to about 30 parts by weight of a quaternary ammonium germicide and iodine complex consisting of from about 0.1 to 0.7 mol of physically-bound elemental iodine per mol of quaternary ammonium germicide which are determinable by thiosulfate titration, and a quaternary ammonium germicide of the group consisting of long-chain alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl phenoxy alkoxy alkyl dimethyl benzyl quaternary ammonium halides, long-chain alkyl pyridinium halides, long-chain alkyl trimethyl quaternary ammonium halides, long-chain alkyl benzyl di-ethyl ethanol ammonium halides and long-chain alkyl benzyl trimethyl ammonium halides, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 0.1 to 50 parts by Weight of a fatty acid lower alkanol amide based on 100 parts by weight of the combined sulfonate and the quaternary ammonium germicide and iodine complex.
8. A germicidal detergent composition consisting essentially of about 95 to about 99 parts by weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl trimethyl quaternary ammonium chloride containing about by weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to '30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfate and the iodine and dodecyl benzyl trimethyl quaternary ammonium chloride complex.
9. A germicidal detergent composition consisting essentially of about 95 to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl trimethyl quaternary ammonium chloride containing about 10% by Weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by Weight of the combined sulfonate and the iodine and dodecyl benzyl trimethyl quaternary ammonium chloride complex.
10. A germicidal detergent composition consisting essentially of from about to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl dimethyl benzyl quaternary ammonium chloride containing about 10% by Weight of physically-bound iodine in elemental form based on the dodecyl benzyl dimethyl quaternary ammonium chloride which is determinable by thiosulfate titration, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfonate and the iodine and dodecyl benzyl dimethyl benzyl quaternary ammonium chloride complex.
11. A germicidal detergent composition consisting essentially of from about 95 to about 99 parts by Weight of an alkali metal alkyl sulfate containing from 12 to 18 carbon atoms in the alkyl group, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physicallybound iodine in elemental form based on the dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being substantially free of unbound iodine as indicated by a negative external starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfate and the iodine and dodecyl benzyl diethyl ethanol quaternary ammonium chloride complex.
12. A germicidal detergent composition consisting essentially of from about 95 to about 99 parts by weight of an alkali metal alkyl benzene sulfonate having from 12 to 15 carbon atoms in the alkyl radical thereof, from about 1 to about 5 parts by weight of a complex consisting of iodine and dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl diethyl ethanol quaternary ammonium chloride present which is determinable by thiosulfate titration, said complex being free of unbound iodine as indicated by a negative starch color test in aqueous medium and about 10 to 30 parts by weight of lauric isopropanol amide based on 100 parts by weight of the combined sulfonate and the iodine and dodecyl benzyl diethyl ethanol quaternary ammonium chloride complex.
13. A liquid germicidal detergent composition consisting essentially of about 45% by weight of sodium lauryl sulfate, about 1% by weight of dodecyl benzyl diethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl di-eihyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 26% by weight of ethanol and about 16% by weight of water.
14. A liquid germicidal detergent composition consisting essentially of about 45% by weight of sodium dodecyl benzene sulfonate, about 1% by weight of dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl di-ethyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 26% by weight of ethanol and about 16% by Weight of water.
15. A liquid germicidal detergent composition consisting essentially of about 45% by Weight of sodium dodecyl benzene sulfonate, about 1% by weight of dodecyl benzyl trimethyl quaternary ammonium chloride containing about 20% by weight of physically-bound iodine in elemental form based on the dodecyl benzyl trimethyl quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium, about 12% by weight of lauric isopropanol amide, about 28% by weight of isopropanol, and about 14% by weight of water.
16. A dry germicidal detergent composition consisting essentially of about 38% by weight of sodium dodecyl benzene sulfonate, about 6% by weight of dodecyl benzyl diethyl ethanol quaternary ammonium chloride containing about 10% by weight of physically-bound iodine in elemental formed based on the dodecyl benzyl diethyl ethanol quaternary ammonium chloride which is determinable by thiosulfate titration, said quaternary and iodine complex being substantially free of unbound iodine as indicated by a negative starch color test in aqueous medium and about 56% by weight of sodium sulfate.
References Cited in the file of this patent UNITED STATES PATENTS
Claims (1)
1. A GERMICIDAL DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF 70 TO 99.5 PARTS BY WEIGHT OF AN ORGANIC ANIONIC DETERGENT OF THE GROUP CONSISTING OF WATER-SOLUBLE ALKALI METAL SALTS OF AN ORGANIC SULFURIC REACTION PRODUCT HAVING IN ITS MOLECULAR STRUCTURE A HIGHER MOLECULAR ALKYL RADICAL OF FROM 8 TO 18 CARBON ATOMS AND A RADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURIC ACID ESTER RADICALS AND 0.5 TO 30 PARTS BY WEIGHT OF A QUATERNARY AMMONIUM GERMICIDE HALOGEN COMPLEX CONSISTING OF FROM ABOUT 0.01 TO 1.0 MOLS OF PHYSICALLYBOUND ELEMENTAL IODINE PER MOL OF QUATERNARY AMMONIUM GERMICIDE WHICH ARE DETERMINABLE BY THIOSULFATE TITRATION, AND A QUATERNARY AMMONIUM GERMICIDE OF THE GROUP CONSISTING OF LONG-CHAIN ALKYL DIMETHLY BENZYL QUATERNARY AMMONIUM HALIDES, LONG-CHAIN ALKYL PHENOXY ALKOXY ALKYL DIMETHYL BENZYL QUATERNARY AMMONIUM HALIDES, LONGCHAIN ALKYL PYRIDINIUM HALIDES, LONG-CHAIN ALKYL TRIMETHYL QUATERNARY AMMONIUM HALIDES, LONG-CHAIN ALKYL BENZYL DI-ETHYL ETHANOL AMMONIUM HALIDES AND LONG-CHAIN ALKYL BENZYL TRIMETHYL AMMONIUM HALIDES, SAID COMPLEX BEING SUBSTANTIALLY FREE OF UNBOUND HALOGEN AS DEMONSTRATED BY ITS FAILURE TO FORM HALOGEN AMINES WHEN EXPOSED TO AMMONIA VAPORS.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US295808A US2746928A (en) | 1952-06-26 | 1952-06-26 | Germicidal detergent compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US295808A US2746928A (en) | 1952-06-26 | 1952-06-26 | Germicidal detergent compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US2746928A true US2746928A (en) | 1956-05-22 |
Family
ID=23139309
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US295808A Expired - Lifetime US2746928A (en) | 1952-06-26 | 1952-06-26 | Germicidal detergent compositions |
Country Status (1)
Country | Link |
---|---|
US (1) | US2746928A (en) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3016327A (en) * | 1955-12-12 | 1962-01-09 | Anderson | Biocidal composition and method |
US3062630A (en) * | 1960-03-23 | 1962-11-06 | Exxon Research Engineering Co | Antistatic additives |
US3105500A (en) * | 1959-08-04 | 1963-10-01 | American Cyanamid Co | Soil retaining finish for textiles |
US3125487A (en) * | 1964-03-17 | Bacteriostatic compositions and meth- | ||
US3141821A (en) * | 1959-03-17 | 1964-07-21 | Lehn & Fink Products Corp | Synergistic combination of alkyl sulfonates, alkylaryl sulfonates and topical antibacterial agents for local antisepsis |
US3152073A (en) * | 1959-12-03 | 1964-10-06 | Michigan Chem Corp | Method for the sterilization of water |
US3216944A (en) * | 1961-09-11 | 1965-11-09 | Procter & Gamble | Stabilized fabric softener composition |
US3240711A (en) * | 1958-10-08 | 1966-03-15 | Wittwer John | Germicidal detergent bar |
US3247119A (en) * | 1962-02-06 | 1966-04-19 | Armour & Co | Cleansing composition and thickener therefor |
US3325404A (en) * | 1963-09-19 | 1967-06-13 | Millmaster Onyx Corp | Composition for simultaneously laundering and softening fabrics |
US3331874A (en) * | 1962-05-29 | 1967-07-18 | Herbert C Stecker | Bistrifluoromethyl anilides |
US3408298A (en) * | 1965-08-18 | 1968-10-29 | Gerdan Chemical Corp | Detergent germicidal compositions |
US3493660A (en) * | 1967-05-15 | 1970-02-03 | Cargill Inc | Bactericidal quaternary ammonium compositions |
US3505221A (en) * | 1966-07-20 | 1970-04-07 | Armour Ind Chem Co | Fabric softener |
US3538520A (en) * | 1967-12-26 | 1970-11-10 | Madison Chem Corp | Lavatory sanitation bodies |
US3997453A (en) * | 1974-02-11 | 1976-12-14 | Colgate-Palmolive Company | Softener dispersion |
US4303543A (en) * | 1979-02-27 | 1981-12-01 | The Procter & Gamble Company | Method for cleansing and conditioning the skin |
US6017561A (en) * | 1997-04-04 | 2000-01-25 | The Clorox Company | Antimicrobial cleaning composition |
US6080387A (en) * | 1998-07-15 | 2000-06-27 | The Clorox Company | Aerosol antimicrobial compositions |
US6436445B1 (en) | 1999-03-26 | 2002-08-20 | Ecolab Inc. | Antimicrobial and antiviral compositions containing an oxidizing species |
US6534075B1 (en) | 1999-03-26 | 2003-03-18 | Ecolab Inc. | Antimicrobial and antiviral compositions and treatments for food surfaces |
US20030185902A1 (en) * | 2002-03-28 | 2003-10-02 | Ecolab Inc. | Antimicrobial and antiviral compositions containing an oxidizing species |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2196985A (en) * | 1934-07-31 | 1940-04-16 | Nat Aniline & Chem Co Inc | Alkyl hydroxy aromatic sulphonates |
US2498174A (en) * | 1945-07-07 | 1950-02-21 | Morris John Carrell | Aluminum hexacarbamide periodide as water disinfectant |
-
1952
- 1952-06-26 US US295808A patent/US2746928A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2196985A (en) * | 1934-07-31 | 1940-04-16 | Nat Aniline & Chem Co Inc | Alkyl hydroxy aromatic sulphonates |
US2498174A (en) * | 1945-07-07 | 1950-02-21 | Morris John Carrell | Aluminum hexacarbamide periodide as water disinfectant |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3125487A (en) * | 1964-03-17 | Bacteriostatic compositions and meth- | ||
US3016327A (en) * | 1955-12-12 | 1962-01-09 | Anderson | Biocidal composition and method |
US3240711A (en) * | 1958-10-08 | 1966-03-15 | Wittwer John | Germicidal detergent bar |
US3141821A (en) * | 1959-03-17 | 1964-07-21 | Lehn & Fink Products Corp | Synergistic combination of alkyl sulfonates, alkylaryl sulfonates and topical antibacterial agents for local antisepsis |
US3105500A (en) * | 1959-08-04 | 1963-10-01 | American Cyanamid Co | Soil retaining finish for textiles |
US3152073A (en) * | 1959-12-03 | 1964-10-06 | Michigan Chem Corp | Method for the sterilization of water |
US3062630A (en) * | 1960-03-23 | 1962-11-06 | Exxon Research Engineering Co | Antistatic additives |
US3216944A (en) * | 1961-09-11 | 1965-11-09 | Procter & Gamble | Stabilized fabric softener composition |
US3247119A (en) * | 1962-02-06 | 1966-04-19 | Armour & Co | Cleansing composition and thickener therefor |
US3331874A (en) * | 1962-05-29 | 1967-07-18 | Herbert C Stecker | Bistrifluoromethyl anilides |
US3325404A (en) * | 1963-09-19 | 1967-06-13 | Millmaster Onyx Corp | Composition for simultaneously laundering and softening fabrics |
US3408298A (en) * | 1965-08-18 | 1968-10-29 | Gerdan Chemical Corp | Detergent germicidal compositions |
US3505221A (en) * | 1966-07-20 | 1970-04-07 | Armour Ind Chem Co | Fabric softener |
US3493660A (en) * | 1967-05-15 | 1970-02-03 | Cargill Inc | Bactericidal quaternary ammonium compositions |
US3538520A (en) * | 1967-12-26 | 1970-11-10 | Madison Chem Corp | Lavatory sanitation bodies |
US3997453A (en) * | 1974-02-11 | 1976-12-14 | Colgate-Palmolive Company | Softener dispersion |
US4303543A (en) * | 1979-02-27 | 1981-12-01 | The Procter & Gamble Company | Method for cleansing and conditioning the skin |
US6017561A (en) * | 1997-04-04 | 2000-01-25 | The Clorox Company | Antimicrobial cleaning composition |
US6270754B1 (en) | 1997-04-04 | 2001-08-07 | The Clorox Company | Antimicrobial cleaning composition |
US6080387A (en) * | 1998-07-15 | 2000-06-27 | The Clorox Company | Aerosol antimicrobial compositions |
US6482392B1 (en) | 1998-07-15 | 2002-11-19 | The Clorox Company | Aerosol antimicrobial compositions |
US6436445B1 (en) | 1999-03-26 | 2002-08-20 | Ecolab Inc. | Antimicrobial and antiviral compositions containing an oxidizing species |
US6534075B1 (en) | 1999-03-26 | 2003-03-18 | Ecolab Inc. | Antimicrobial and antiviral compositions and treatments for food surfaces |
US20030185902A1 (en) * | 2002-03-28 | 2003-10-02 | Ecolab Inc. | Antimicrobial and antiviral compositions containing an oxidizing species |
US6855328B2 (en) | 2002-03-28 | 2005-02-15 | Ecolab Inc. | Antimicrobial and antiviral compositions containing an oxidizing species |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2746928A (en) | Germicidal detergent compositions | |
USRE23840E (en) | Liquid anionic-dialkylolamide | |
US2787595A (en) | Sulfoxide containing detergent compositions | |
DE1767334A1 (en) | Foam-regulated washing active substance combination or detergent containing them | |
DE2051554A1 (en) | Preparations for the production of cold bleaching liquors, in particular washing liquors with a cold bleaching effect | |
US2469493A (en) | Synthetic detergent composition | |
US4751009A (en) | Fabric softeners comprising stable single phase clear solutions of anionic and cationic surfactants | |
JPH05509111A (en) | Pumpable flowable liquid surfactant-rich formulation | |
US2904468A (en) | Skin disinfectant containing polyoxyethylene alkyl phenol, calcium chelating agent and either an organic sulfate or sulfonate salt | |
US2864679A (en) | Selective method of inhibiting preemergent growth of grasses | |
DE1942236A1 (en) | Enzymatic washing agents and detergents | |
US2712530A (en) | Sulfonate detergent blend | |
JPS609557B2 (en) | Novel liquid cleaning composition | |
Ernst | Surface active betaines as protective agents against denaturation of an enzyme by alkyl sulfate detergents | |
DE1949561C3 (en) | Abrasives with bleaching and disinfecting properties | |
US2702774A (en) | Process of preparation of free flowing composition containing quaternary ammonium compound | |
DE2039450A1 (en) | Antimicrobial bleaching textile treatment agents | |
US3345301A (en) | Pourable and free-flowing detergent, wetting, and emulsifying compositions | |
US2721847A (en) | Synthetic detergent composition | |
US3390096A (en) | Combinations of wash-active substances in liquid or paste form | |
DE1940654A1 (en) | Enzymatic detergent | |
US3283005A (en) | p-xylylene bis quaternary ammonium compounds | |
US3586632A (en) | Cleaning compositions containing curd dispersants | |
DE2025944A1 (en) | Detergent compsns for textiles - with combined cleaning - and softening actions,contng quaternary ammonium salts of unsatd carb | |
US2383739A (en) | Detergent composition |