Antimicrobial detergent composition containing aminopolyureylene resin
I United States Patent 1191 [11] 3,875,071  
 Grand Apr. 1, 1975 ANTIMICROBIAL DETERGENT 3311.594 3/1967 Earle 260/775 CO O CONTAINING 3,489,686 1/1970 Parrun 252/106 3.506.720 4/1970 Model et a1 252/106 AMINOPOLYUREYLENE RESIN 3,668,135 6/1972 Nosler et a1. 252/106 [75] Inventor: Paul Sheldon Grand, South Bound 3.681.249 8/1972 Traber ct a1. 252/106 B k NJ 3.725.547 4/1973 Kooistra 252/106 [73] Assignee: colgf&#39;te&#39;palmolive Company New Primary Eraminer-Leland A. Sebastian York Assist/111! E.\an1ine/&#39;E. A. Miller 22 i 22 1972 Attorney, Agent, or Firn1Richard N. Miller; Ronald S. Cornell; Herbert S. Sylvester [21] Appl. No.: 308,884  
  Related US. Application Data 1 1 ABSTRACT [62] Division of SCI. N6. 90154. Nov. 16. 1970. Put. NO. Detergent Compositions Comprising a mixture Of 3,726,815. 2-9992 by weight of a water-soluble organic detergent, 0.05 to 5 percent by weight of an aminopolyureylene [52] US. Cl. 252/106, 252/544 resin halving :1 molecular weight in the range of about [51] Int. Cl Clld 3/48 300 t 0 00 d 0- 5 to 5 p nt y ig t of a [58] Field of Sear h 352/1()6 544 water-soluble or water-insoluble antimicrobial agent. Preferred compositions contain 10 to 40 percent by [56] References Cited weight of detergent 0.5 to 3.5 percent by weight of UNITED STATES PATENTS resin. 0.1 to 3 percent by weight of antimicrobial 3,156,672 11/1964 vim def Kerk (H211 260/775 and 3.240.664 3/1966 Earle 162/164 9 Claims, No Drawings ANTIMICROBIAL DETERGENT COMPOSITION CONTAINING AMINOPOLYUREYLENE RESIN This is a divisional, of application Ser, No. 90,154  
 filed Nov. 16, 1970, now US. Pat. No. 3,726,815.  
  The invention relates to improved compositions comprising a water-soluble and/or water-insoluble active material having the capacity to impart a residual characteristic to surfaces treated therewith such as antibacterial compounds, tarnish inhibitors, ultra-violet absorbers, fluorescent brighteners, bluing agents and skin treating materials and an aminopolyureylene (APU) resin in an amount effective to enhance the effects of the active materials. The APU resins appear to enhance the deposition and/or retention of thewater-soluble and waterinsoluble active substances on the surfaces contacted therewith.  
  The capacity of the APU resin to improve the effectiveness of the active materials on surfaces contacted therewith surprisingly is maintained in the presence of water-soluble organic detergents and, therefore, detergent compositions containing the mixture of active material and APU resin represent preferred embodiments. Such detergent compositions include dishwashing detergents, shampoos, laundry detergents, hardsurface cleaners and toilet bars. The effectiveness of the APU resins in the presence of minor and major amounts of watersoluble organic detergents is surprising because the effectiveness of the active materials is due to the deposition and/or retention of the active materials on surfaces contacted therewith and detergents normally tend to minimize deposition and retention of such materials on the washed surfaces. Thus, usually only a small percentage of the active materials in a detergent composition is actually retained ona particular surface or substrate after washing and, optionally, rinsing. Accordingly, to achieve a particular level of activity, the concentrations of active material must be increasedwith an attendant increase in cost when used as a component in a detergent composition.  
  While the mechanism by which the improved effects are obtained is not understood, it appears that the APU resin may unite either with the active material or&#39;thecontacted surface to increase the affinity of the active material for the surface. In many cases, an increase in the weight of active material retained by the surface has been quantitatively verified. However, no absolute mechanism has been defined and the invention is not limited to any particular theory.  
  Generally, the improved compositions of this invention consist essentially of a mixture of i an aminopolyureylene resin having a molecular weight in the range of about 300 to 100,000 and a water-soluble or water-insoluble active material having the capacity to impart a residual property to surfaces treated therewith and selected from the group consisting of (A) antibacterial compounds, (B) tarnish inhibitors, (C) ultraviolet absorbers, (D) optical brighteners, (E) bluing agents and (F) skin-treating compounds, the weight ratio of resin to active material being effective to improve the effects of the active material and selected from the range of 1:1 to :1 preferably 1:1 to 5:1. Preferred compositions are detergent compositions comprising 2% to 99% by weight of a water-soluble, organic detergent, 0.05% to 5% by weight of aminopolyureylene resin and about 0.05 to 5% by weight of active material.  
  Also, within the scope of the invention is a method for improving the effectiveness of active materials on surfaces contacted therewith which comprises contacting the surface with a water solution or dispersion of 5 the active material and an effective amount of the aminopolyureylene resin sufficient to improve the effect of the active material retained on the treated surface after the contacting solution is removed.  
  The APU resins suitable for use in the described compositions and method have a molecular weight. in the range of about 300 to 100,000 and are characterized by the following repeating unit: -[-(CI-I ),,X- (CH ),,NHC(Y)NH+ wherein X is NH, NC to C alkyl, 7  
  en ca 4.2 2;; \CH2 CH2,  
  Generally, the number of repeating units in the resin will be sufficient to yield a polymer having a molecular weight in the range of about 300 to 100,000. Preferred APU resins have an average molecular weight in the range of 1,000 to 20,000 and a particularly preferred resin is the reaction product of equimolar quantities of N-methyl, bis(3-amino-propyl) amine and urea having a molecular weight of about 4,300.  
 The molecular weight of the APU resins is based upon aqueous gel permeation chromatographic analysis. The separation is carried out in oxalic acid solution, adjusted to pH 3.5, on three Corning controlled-pore glass columns (nominal pore sizes 175,125 and 75A) in series. Detection is by differential refractometer. Reference compounds are dextran polysaccharides of molecular weights of 150,000, 110,000, 40,000, 20,000 and 10,000 and sucrose and galactose.  
  The APU resins which can be used in the compositions of this invention are prepared by reacting, for example, 145 grams of N-methyl bis (3-aminopropyl) amine (1.0 mole) and grams of urea (1.0 mole) in a 3-necked flask equipped with a therometer, mechanical stirrer, condenser, and nitrogen sparge tube. Nitrogen is bubbled slowly through the solution throughout the course of the reaction. The solution is heated to piperazine or N,N-di (2-aminoethyl) piperazine with urea or thiourea. The&#39;N-C, to C alkyl analogues are prepared by reacting N-C to C alkyl bis(3- aminopropyl) amine or N-C to C alkyl bis(2- aminoethyl) amine with urea or thiourea. Additional analogues are prepared by the following reactions:  
  CH3 Resin A I epichloronydrin ll analogues GH -220x 01 p11 P 3 1 q+ analogues Na0H -9 F analogues CH CH-Cl&#39;l CHQ CHCHQCI. 2 2  
 till  
 CH 3 analogues 9 3 M H 0 N&#39;*&#39; analogues l 2 &#34;Mi-3 caggn-cngon 0 OH e Ruin A dimethyl sulfate rr&#39; analogues The preparation of theremaining analogues is well within the skill of the art following the above techniques.  
  The active materials which are potentiated by the APU resin are well known and have been used for treating surfaces and substrates to impart certain residual characteristics to the contacted surfaces. The treated surfaces or substrates include proteinaceous materials such as hair and skin, textiles such as cotton, rayon and synthetic fibers, and porcelain, wood, plastic and metal. Such active materials may be water-soluble such as cetyl dimethyl benzyl ammonium bromide and gelatin or water-insoluble such as zinc Z-pyridinethioll-oxide and optical brighteners. To facilitate activity and utility, the water-insoluble materials are usually in the form of finely divided particles having a diameter in the range of about 0.5 to 50 microns. Suitable active materials include antibacterial compounds, tarnish inhibitors, ultra-violet absorbers, optical brighteners, bluing agents and skin treating materials such as hydrolyzed proteins, silicones and polyacrylamides.  
  Antibacterial compounds which may be used in the compositions include water-soluble and waterinsoluble salts of Z-pyridinethiol-l-oxide, substituted salicylanilides, substituted carbanilides, halogenated bisphenols, mono-higher alkyl quartemary ammonium salts, and 5,7diiodo-8-hydroxyquinoline.  
  Preferred antibacterial compounds include the waterinsoluble salts, e.g., zinc, cadmium, zirconium,tin and aluminum, and water-soluble salts, e.g., sodium and potassium, of Z-pyridinethiol-l-oxide which has the following structural formula in tautomeric form.  
 The zinc and sodium salts of Z-pyridinethiol-l-oxide are particularly preferred.  
  Other suitable antibacterial compounds are the substituted bisphenols having the formula wherein Y is hydrogen, halogen, or trifluoromethyl and- Z is hydrogen or halogen. Among the suitable salicylanilides are 3,4&#39;,5 tribromosalicylanilide; 5-  
  bromosalicyl 3,5 di(trifluoromethyl)anlide; 5 chlorosalicyl 3,5 di(trifluoromethyl)anlide; 5 3,5 di(trifluoromethyl)anlide; 3,5 -dichlorosalicyl 3,4 dichloroanilide; and 5 chlorosalicyl 3 trifluoromethyl 4 chloroanilide, These and other useful salicylanilides are disclosed in U.S. Pat. No. 2,703,332.  
  Satisfactory substituted carbanilides have the following general structure Y O Y H Q- NH. 0- NH- wherein Y is hydrogen, halogen, or trifluoromethyl, W is halogen or ethoxy, and W is hydrogen or halogen.  
  Included among the suitable carbanilides are 3,4,4 trichlorocarbanilide; 4,4-trifluoromethyl 3&#39;4,4&#39; trichlorocarbanilide; 3,3 bis(trifluoromethyl 4 ethoxy 4 chlorocarbanilide; and 3,5 bis(trifluoromethyl) 4&#39; chlorocarbanilide.  
 wherein R, is C, to C alkyl, R and R are each C, C, alkyl, R is C, C alkyl or benzyl and A is an anion selected from the group consisting of chlorine, bromine, iodine, and methosulfate. A preferred compound is cetyl trimethyl ammonium bromide.  
  Additional useful antimicrobial compounds include 5,7-diiodo-8-hydroxy quinoline, 1,6- di(4&#39;chlorophenyl-diguanado) hexane, and 5-chloro- 2(2,4-dichlorophenoxy)phenol, C to C isoquinolinium halides, such as&#39;lauryl isoquinolinium bromide, and C C alkyl pyridinium halide.  
  The tarnish inhibitors potentiated by APU resins include, for example, benzotriazole and ethylenethiourea.  
  Ultraviolet absorbers potentiated by APU resins have the structural formula where X, Y, and Z are selected from the group consisting of hydrogen, hydroxy, C, to C alkoxy and carboxy, at least one of said X, Y, and Z being oxy. Preferred compounds include 2-hydroxy-4-n-octoxybenzophenone and 2-hydroxy -4-methoxy-2-carboxybenzophenone.  
  The optical or fluoroescent brightener active materials which are potentiated by the APU resins are selected from the group consisting of stilbene disulfonates, quatemized aminoalkyl substituted phenyl sulfonamides of aryl pyrazolines, substituted styrylnaphth o);- azoles, and substituted aminocoumarins.  
 Suitable stilbene disulfonate fluorescent brighteners have the formula C N\ N C n c-NHQ CH=CH- Ant-c =N \N=C l I x so r: 0 K  
 ea er- 0H CHZCHEOH 6 Suitable compounds are disodium 4,4 bis [4-anilino-6- methoxyanilino-s-triazin-Zyl amino]-2 ,2&#39; stilbene disulfonate and disodium 4,4 bis (4,6 dianilino-s-triazin-2yl amin&#39;o) 2,2 stilbene-disulfonte.  
 Suitable quatemized aminoalkyl substituted phenyl sulfonamides of aryl pyrazoline have the following formula:  
 X HC N wherein X is hydrogen, phenyl, or halogenated phenyl with not more than one X being hydrogen and Y is a quaternized ia cn= cn- Q wherein A and B are different and represent oxygen and nitrogen, and R represents individually hydrogen, alkyl groups having 1 to 6 carbon atoms, chlorine or fluorine. A preferred oxazole brightener is 2- strylnaphth (1,2-d) oxazole.  
 Additional fluorescent brighteners potentiated by APU resin are the water-soluble substituted aminocoumarins having the following structural formula:  
  H R\ i) ,=:0 R/ Y wherein R is hydrogen or C, C alkyl. A preferred compound is 4 methyl, 7 dimethyl amino coumarin.  
  A bluing material which is potentiated by APU resin is ultramarine blue. This is a well-known blue pigment occurring naturally as mineral the lapis lazuli. It can be.  
 made, for example, by igniting a mixture of kaolin, sodium carbonate or sulfate, sulfur, and carbon. It is insoluble in water and is stable when in contact with wherein X is OH, DIE-Q CH ----CH&#39; N/ 2 0 or Nii .ocn and Y is Nit-Q n(c r cn oH) or @ocn bleaching agents, alkali, and light. Details for synthetic ultramarines are given in the text fUltramarines, Their&#39; History and Characteristics, Reckitts (Colours) Ltd., Hull, England. Preferred -are micropulverized, syntheticultramarine blues, particularly grades-RS4g-RS8 provided by Reckitts. The pigment is in the form of par-1 ticles substantially all of which exhibit a diameter of less than about 0.05 millimeter, and is characterized by the ability to impart a faint blue visible shade to fabrics treated therewith without staining such fabrics when used at recommended concentration and fashion, being generally considered to be non-substantive, or at least non-accumulative, on fabrics. r  
 The skin-treating materials which are teins. Such proteins are substantive to the hair and skin in the presence of detergents. Suitable proteins are watersoluble polypeptides, having a molecular weight in the range of about 120 (amino acid to about 20,000, preferably from about 800 to 12,000. Such polypeptides are obtained by hydrolysis of protein rna terials such as hides, gelatinjcollagen, and the like, with collagen protein being preferred, using wellknown processes. During hydrolysis the protein materials are gradually broken down into their constituent polypeptides and amino acids by prolonged heating with acids, e.g., sulfuric acid, or alkalis, e.g., sodium hydroxide, or treatment with enzymes, e.g., peptidases. First, high molecular weight polypeptides are formed, and as hydrolysis proceeds these are converted progressively to simpler and simpler polypeptides, to tripeptides, dipeptides, and finally to amino acids. It is&#39;obvious that the polypeptides derived from proteins are complex mixtures. The preferred hydrolysates are ob; tained. from boneor skin-derived collagen protein by enzymatic hydrolysis and are sold under the trade;  
 ionic, polar nonionic, and cationic detergents, and mixtures of two or more of the foregoing detergents.  
 The anionic surface-active agents include those surfaceactive or detergent compounds which contain an.  
 organic hydrophobic group containing generally 8 to 26 carbon atoms and preferably .10 to 18 carbon atoms in their molecular structure, and at least one watersolubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.  
  enhanced by the APU resins are the water-soluble, substantive pro- 8 tures derived from coconut oil and tallow, for example, sodium coconut soap and potassium tallow soap.  
 The anionic class of detergents also include the water-soluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, and preferably &#39;as the higher akyl ber&#39;izene sulfonates containing from to 16 carbon atoms in the higher alkyl group in a straight or branched chain, for example, the sodium, potassium, and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene&#39;sulfonates, higher alkyl phenol sulfonates and higher naphthalene sulfonates, A preferred sulfonate is linear alkyl benzene sul fonate having a high content of 3- (or higher)phenyl isomers and a correspondingly low content (well below 50 percent) of 2- (or .lower) phenyl isomers, that is, wherein the benzene ring is preferably attached in large part at the 3 or higher&#39;(for example, 4, 5, 6 or 7) position of the alkyl group and the content of the isomers in which the benzene ring is attached in the 2 or 1&#39; position is correspondingly low. Particularly preferred materials are set forth in US. Pat. No. 3,320,174.  
  Other suitable anionic detergents are the olefin sulfonates, including long-chain alkene sulfonates, longchain hydroxyalkane sulfonates or mixtures&#39;of alkene sulfonates and hydroxylalkane sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of 80;, with long-chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCH=CHR where R is a higher alkyl group of 6 to 23 carbons and R is an alkyl group of l to 17 carbons or hydrogen to form a mixture of sultones and alkene sulfonic acids which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates &#39;containing about 10 to 20 and preferably about 15 to 20 carbon atoms, for example, the primary paraffin sulfonates arev made by reacting long-chain alpha olefins andbisulfites and paraffin sulfonates having the sulfo-j nated group distributed along-the paraffin chain as shown in US. Pat. Nos; 2,503,280; 2,507,088;  
 3,260,741 3,372, 188; and German Patent 735,096; so-  
 dium and potassium sulfates of higher alcohols containing 8 to 18 carbon atoms such as sodium lauryl sulfate and sodium tallow alcohol sulfate; sodium and potas: sium salts of a-sulfofatty acid esters containing about 10m 20 carbon atoms in the acyl group, for example, methyl a-sulfomyristate and methyl a-sulfotallowate, animoniumsulfatesof monoor di-glycerides of higher (C C fatty acids, for example, stearic monoglyceride monosulfate; sodium and alkylolammonium salts of alkyl polyethenoxy ether sulfates produced by condensing l to 5 moles of ethylene oxide with one mole of higher (C -C alcohol; sodium higher alkyl (C Examples of suitable anionic detergents which fall within the scope of the anionic detergent class&#39;in&#39;cl&#39;ude the water-soluble salts, for example, the sodium, ammonium, and alkylolammonium salts, of higher fatty acids or resin salts containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example, tal&#39;low, grease, coconut oil, tall oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mix- C glyceryleth er sulfonates; and sodium or potassium alkyl phenol pplyethenoxy ether sulfates with about 1 to 6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.  
  The suitable anionic detergents include also the C to C acyl sarcosinates (for example, sodium lauroyl sarcosinate), sodium and potassiumsalts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid,  
 and sodium and potassium salts of the C to C acyl N- methyl taurides, for example, sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.  
  Anionic phosphate surfactants in which the anionic solubilizing group attached to the hydrophobic group is an oxyacid of phosphorous are also useful in the detergent compositions. Suitable phosphate surfactants are the sodium, potassium, and ammonium alkyl phosphate esters such as (R-O) PO M and ROPO M in which R represents an alkyl chain containing from about 8 to 20 carbon atoms or an alkyl phenyl group having 8 to 20 carbon atoms and M represents a soluble cation. The compounds formed by including about 1 to 40 moles of ethylene oxide in the foregoing esters, for example, [R-O(EtO)n] PO M, are also satisfactory.  
  The particular anionic detergent salt will be suitably selected, depending upon the particular formulation and the proportions therein. Suitable salts include the ammonium, substituted ammonium (mono-, di-, and triethanolammonium), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts. Preferred salts are the ammonium, triethanolammonium, sodium, and potassium salts of the higher alkyl sulfates and the C to C acyl sarcosinates.  
  The nonionic synthetic organic detergents are generally the condensation product of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. Further, the length of the polyetheneoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.  
  The nonionic detergents include the polyethylene oxide condensate of one mole of alkyl phenol containing from about 6 to 12 carbon atoms in a straightor branched-chain configuration with about to 30 moles of ethylene oxide, for example, nonyl phenol condensed with 9 moles of ethylene oxide, dodecyl phenol condensed with 15 moles of ethylene and dinonyl phenol condensed with 15 moles of ethylene oxide. Condensation products of the corresponding alkyl thiophenols with 5 to 30 moles of ethylene oxide are also suitable.  
  Still other suitable nonionics are the polyoxyethylene polyoxypropylene adducts of l-butanol. The hydrophobe of these anionics has a minimum molecular weight of 1,000 and consists of an aliphatic monohydric alcohol containing from 1 to 8 carbon atoms to which is attached a heteric chain of oxyethylene and oxypropylene. The weight ratio of oxypropylene to oxyethylene covers the range of 95:5 to 85:15. Attached to this is the hydrophilic polyoxyethylene chain which is from 44.4 to 54.6 of the total molecular weight.  
  Also included in the nonionic detergent class are the condensation products of a higher alcohol containing about 8 to 18 carbon atoms in a straight or branchedchain configuration condensed with about 5 to 30 moles of ethylene oxide. for example, lauryl-myristyl alcohol condensed with about 16 moles of ethylene oxide.  
  A particularly useful group of nonionics is marketed under the trade name Pluronics. The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 1,200 to 2,500. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole. The molecular weight of the block polymers varies from 1,000 to 15,000, and the polyethylene oxide content may comprise 20 to 80 percent by weight.  
 Zwitterionic detergents such as the betaines and sulfobetaines having the following formula are also useful:  
 wherein R is an alkyl group containing about 8 to 18 carbon atoms, R and R are each an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms, R is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, and X is C or 8:0. The alkyl group can contain one or more intermediate linkages such as amido, ether, or polyether linkages or nonfunctional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group. When X is C, the detergent is called a betaine; and when X is 5:0, the detergent is called a sulfobetaine or sultaine. Preferred betaine and sulfobetaine detergents are l-(lauryl dimethylammonio) acetate, l-(myristyl dimethylammonio) propane-3- sulfonate, and l-( myristyldimethylammonio )-2- hydroxy-propane-3-sulfonate.  
  The polar nonionic detergents are those in which the hydrophilic group contains a semi-polar bond directly between two atoms, for example, N O, P 0, As O, and S *&#39;O. There is charge separation between the two directly bonded atoms, but the detergent molecule bears no net charge and does not dissociate into ions.  
  The polar nonionic detergents of this invention include open-chain aliphatic amide oxides of the general formula R R R N O. For the purpose of this invention R is an alkyl, alkenyl, or monohydroxyalkyl radical having about 10 to 16 carbon atoms, R and R are each selected from the group consisting of methyl, ethyl, propyl, ethanol, and propanol radicals.  
  Other operable polar nonionic detergents are the openchain aliphatic phosphine oxides having the general formula R R R P 0 wherein R is an alkyl, alkenyl, or monohydroxyalkyl radical ranging in chain length from 10 to 18 carbon atoms, and R and R are each alkyl and monohydroxyalkyl radicals containing from 1 to 3 carbon atoms.  
  Examples of suitable ampholytic detergents include the alkyl beta-aminopropionates, RN(H)C H COOM; the alkyl betaiminodipropionates, RN(C H COOM) the alkyl and hydroxy alkyl taurinates, RN(CH )C H SO M; and the long-chain imidazole derivatives having the following formulas:  
 wherein R is an acyclic group of about 7 to 17 carbon atoms, W is selected from the group of R OH, R COOM, and R OR COOM, Y is selected from the group consisting of OH,R OSO ,R is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, R, is selected from the group consisting of alkyl, alkyl aryl and fatty acyl glyceride groups having 6 to 18 carbon atoms in the alkyl or an acyl group; and M is a water-soluble cation, for example, sodium, potassium, ammonium, for alkylolammonium.  
  Formula I detergents are disclosed in Volume II of Surface Active Agents and Detergents and Formula 11 detergents are described in US. Pat. No. 2,773,068; US. Pat. No. 2,781,354; and US. Pat. No. 2,781,357. The acyclic groups may be derived from coconut oil fatty acids (a mixture of fatty acids containing 8 to 18 carbon atoms), lauric fatty acid, and oleic fatty acid, and the preferred groups are C to C alkyl groups. Preferred detergents are sodium N-lauryl betaaminopropionate, disodium N-lauryl iminodipropionate, and the disodium salt of 2-lauryl-cycloimidium 1- hydroxyl, l-ethoxyethanoic acid, l-ethanoic acid.  
  Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.  
  Examples of suitable synthetic cationic detergents are normal primary amines RNl-l wherein R is C to C; the diamines such as those of the type RNHCJ-LNH wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-Z-aminoethyl stearyl amine and N-Z-aminoethyl myristyl amine; amidelinked amines such as those of the type R CONHC H NH wherein R is an alkyl group of 8 to 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-amino ethylmyristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 8 to 22 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including alkyl groups bearing inert substituents, such as phenyl groups, and there is present an anion such as halogen, acetate, methosulfate, etc. The alkyl group may contain intermediate linkages such as amide which do not substantially affect the hydrophobic character of the group, for example, stearyl amido propyl quaternary ammonium chloride. Typical quaternary ammonium detergents are ethyl-dimethylstearyl ammonium chloride, benzyl-dimethylstearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propylmyristyl ammonium chloride, and the corresponding methosulfates and acetates.  
  Preferred detergent compositions of this invention are the liquid, antimicrobial shampoo compositions suitable for washing the hair and scalp. Such compositions consist essentially of about 10 to 40 percent by weight of a detergent selected from the group consisting of non-soap anionic, amphoteric, and zwitterionic detergents from 0.1 -to 3 percent by weight of watersoluble or water-insoluble particulate antimicrobial active material, 0.5 to 3.5 percent of aminopolyureylene resin, and the balance primarly water. The shampoo compositions may also include minor amounts of ethanol or isopropanol perfume, color, stearate opacifying agents, ethylene diamine tetracetate or citrate sequestering agents, thickening agents, and fatty acid alkylolamide foam boosters.  
  Other detergent compositions falling within the scope of the invention are the heavy-duty laundering compositions containing APU polymers and at least one of the active materials potentiated by the polaminopolyureylene resins, such as antibacterials, fluorescent brighteners, and bluing agents. Such compositions generally consist essentially of about 8 to 40 percent by weight of non-soap anionic or nonionic detergent, about 0.1 to 3 percent by weight of active material, about 0.5 to 3.5 percent by weight of APU resin and the balance water-soluble inorganic or organic builder salt. Suitable builders include sodium sulfate, sodium carbonate, and sodium nitrilotriacetate as well as the corresponding potassium compounds. Other compositions are sodium carboxymethylcellulose, polyvinylalcohol, perfume, color, etc.  
  The foregoing laundering detergents may also be prepared in liquid form. Suitable liquids consist essentially of about 5 to 20 percent by weight of non-soap anionic or nonionic detergent, 10 to 25 percent by weight of potassium pyrophosphate, sodium silicate or sodium nitrilotriacetate, 4 to 12 percent by weight of sodium or potassium xylene or toluenesulfonate, 0.1 to 3.0 percent by weight of active material, 0.5 to 3.5 percent by weight of APU resin, and the balance primarily water. Suitable additives which may be added are sodium carboxymethylcellulose, thickeners, color, and perfume.  
  In bar form, the detergent material may be soap, anionic, amphoteric, nonionic or mixtures of the foregoing detergents. In addition to the usual proportions of APU resin and active material, the bars may include color, perfume, free fatty acids, sodium chloride, and fatty acid alkanolamide suds builders.  
  Each of the foregoing detergent compositions can be prepared by methods well known in the art. For example, shampoos and built liquid detergents are prepared by mixing, and particulate laundering detergents are prepared by mixing, chemical drying or spray drying.  
  The ability of the APU resins to potentiate the deposition of the water-insoluble materials which function as antibacterial agents onto proteinaceous substrates, such as hair and skin, is demonstrated in the following radioactive substantivity test. Substantivity is determined by stirring a 1.27-centimeter diameter circular gelatin disk weighing about 40 milligrams for about five minutes in 10 grams of an aqueous medium containing a known concentration of radioactive tagged material such as zinc Z-pyridinethiol-l-oxide, rinsing the disk five times in 10 milliliters of water, drying, and measuring the radiation emission with the aid of a radiation detector. The absolute degree of deposition of the material is determined by comparing the observed counts with the counts emitted by a known weight of the radioactive material. The effect of APU resin on deposition can be readily ascertained by repeating the test with a known weight of APU present. Similarly, the effect of detergents can be quantitatively measured by including detergents in the test composition.  
  The following examples are illustrative of the compositions falling within the scope of this invention.  
 EXAMPLE 1 An aqueous dispersion of zinc 2-pyridinethiol-loxide is prepared by dispersing 0.04 grams of radioactive zinc Z-pyridinethiol-l-oxide containing zinc 65 in one gram of water. The resultant aqueous dispersion is diluted with 8.96 grams of water with agitation, and the substantivity of the diluted dispersion is determined using the foregoing substantivity procedure. The results of the evaluation indicate 40.9 micrograms of zinc-2-pyridinethiol-l-oxide are deposited on the disk from the aqueous mixture containing 0.4 percent by weight of the Z-pyridinethiol-l-oxide. When the foregoing experiment is repeated in the presence of an amino polyureylene resin (Resin A) having a molecular weight of about 4,300 and the repeating unit (CI-l N(CH )(C1-1 N(H)C(O)N(1l)-, 122 micrograms of zinc 2-pyridinethiol-l-oxide are deposited on the disk at a concentration of 0.5 percent of said resin in the aqueous test dispersion. Thus, the presence of 0.5 percent of APU resin results in a 200 percent increase in the deposition of zinc-2-pyridinethiol-l-oxide from an aqueous medium.  
  Use of a resin having a molecular weight of about 5,600 and N,N&#39;-di(3-aminopropyl) piperazine as the repeating unit in the foregoing test yields comparable results.  
 EXAMPLE 2 When the procedure of Example 1 is repeated using an aqueous solution of 0.25 percent by weight of radioactive (C-14) cetyl trimethylammonium bromide (CTAB) at pH 4.5 as the test medium, 294 micrograms of CTAB are deposited on the gelatin disk. Repetition of this test in the presence of 0.75 percent by weight of the APU resin used in Example 1 results in the deposition of 679 micrograms of CTAB, an increase in deposition of about 130 percent. When the pH of the test solution is increased to 8.5, a deposition of 259 micrograms of CTAB is obtained in the absence of APU resin and a deposition of 734 micrograms is obtained in the presence of 3 percent by weight of the APU resin of Example 1. Thus, a 180 percent increase in deposition of CTAB is noted at pH 8.5.  
 EXAMPLE 3 Example 2 is repeated with the exception that a percent aqueous ethanol mixture is substituted for water in the test solution and the pH is adjusted to 6.5. A deposition value of 202 micrograms of CTAB is noted in the absence of APU resin, and a deposition value of 643 micrograms of CTAB is noted in the presence of 0.73 percent by weight of the APU resin of Example This represents an increase in deposition of about 220 percent. For comparison, only 227 micrograms of CTAB are deposited when the concentration of CTAB in the test solution is increased to 1 percent by weight. Thus, the APU resin is significantly more effective in enhancing deposition than an increase in the CTAB concentration from 0.25 to 1 percent, a 300 percent increase.  
 EXAMPLE 4 When the procedure of Example 1 is repeated using a 0.5 percent-by-weight aqueous alcoholic dispersion of radioactive (C-l4) bis(3,5,6 trichloro-2- hydroxyphenyl) methane as the test solution, the radioactivity of the gelatin disk averages 2,100 counts per minute (cpm.) Repetition of the test in the presence of 1.25% concentration of the APU resin of Example 1 results in an average radioactivity of 13,200 cpm. Thus, the presence ot the APU resin increases the deposition of the antimicrobial compound by about 500%. Substantially similar results are noted when either lamb skin or human callus tissue is substituted for the gelatin disk in the foregoing experiment.  
  The APU resin of Example 1 can be replaced by either a resin having a molecular weight of about 4,600 and the repeating unit +Cl-l N (Cl-1 (CI-1 NH- C(O)NH-lor a resin having a molecular weight of about 6,700 and the repeating unit with substantially similar results. Similarly, the substituted methane may be substituted with 5-chloro- 2(2,4dichlorophenoxy) phenol with substantially similar results.  
 EXAMPLE 5 Tests of the following shampoo illustrate the improved effects attributable to the APU resin. This shampoo is effective to inhibit the growth of Pityrosporum ovale.  
 MEL  
 Triethanolamine lauryl sulfate 10 Lauryldimethyl amine oxide 10 Cocornonoethanol amide 5 Ethyl alcohol 10 Zinc Z-pyridinethiol-l-oxide 1.6 Resin A&#34;&#34; 2.0 Water Balance &#34;Arninopolyureylcnc resin having a molecular weight of about 4,300 and a repeating unit of{(CH,),N(CH=)(CH=)=N(H)C(O)N(H)+ When the foregoing composition is formulated with a radioactive zinc 2-pyridinethiol-l-oxide (Zn 65) material and is evaluated using the substantivity procedures of Example 1, 20.8 micrograms of radioactive zinc 2-pyridinethiol-1-oxide are noted on the gelatin disk. In this evaluation, 2.5 grams of shampoo are diluted with 7.5 grams of water to simulate normal use dilution of shampoos, and the diluted shampoo is test solution. Under such conditions, the concentration of zinc 2-pyridinethiol-1-oxide in the test solution is 0.4 percent by weight, and the concentration of APU resin is 0.5 percent by weight. Repetition of the foregoing test with an identical composition not containing APU resin results in the deposition of 8.7 micrograms of zinc 2-pyridinethiol-l-oxide. Thus, use of APU resin in combination with zinc Z-pyridinethiol-l-oxide in the presence of detergents results in an increase in deposition of about percent.  
  To confirm that increased deposition results in enhanced residual activity, radioactive disks obtained using the foregoing evaluation technique are plated in a standard agar medium inoculated with P. ovale, and the diameters of the zone of inhibition are measured after 24 hours of incubation. These results are shown in Table I together with results of non-radioactive disks. Resin A alone has no zone of inhibition.  
 Table I Zinc 2 Zone of inhibition pyridinethiol-l-oxide APU resin after 24 hours (m.m.)  
 Radioactive No 249 Radioactive Yes 40.3 Non-radioactive No 20.l Non-radioactive Yes 43.5  
 The foregoing results indicate that APU resin significantly improves the antibacterial effectiveness of the zinc 2-pyridinethiol-l-oxide. Further, the results show that radioactivity has a minimal effect on the results.  
  The effect of APU resin on long-standing activity is illustrated by repeatedly transferring the radioactivity disks of Table I to freshly seeded agar plates inoculated with P. ovale for additional incubation periods after measuring the zone of inhibition. Results are set forth in Table II.  
 Table 11 Zone of inhibition (m.m.)  
 APU One Two Three Resin Incubation lncubations lncubations No 24.9 5.8 Yes 43.5 24.5 9.4  
 These results indicate that the presence of APU resin results in improved antimicrobial effectiveness of the zinc-2-pyridinethiol-l-oxide and longer-lasting effectiveness.  
 EXAMPLE 6 Example is repeated with the exception that the concentration of zinc Z-pyridinethiol-l-oxide in the shampoo is reduced to 0.4 percent. 17.4 micrograms of zinc 2-pyridinethiol-1-oxide are deposited on the disk. In the absence of the 2 percent of APU resin, 6.1 micrograms of zinc Z-pyridinethiol-l-oxide are deposited on the disk. Again, APU resin significantly enhances the deposit of zinc Z-pyridinethiol-l -oxide on a proteinaceous substrate.  
 EXAMPLE 7 The following liquid detergent composition is an effective antimicrobial detergent.  
 Sodium lauryl triethenoxy ether sulfate 8.0  
 Lauryl dimethyl amine oxide 7.5  
 Sodium Z-pyridinethiol-l-oxide 2.0  
 Resin A 1.0  
 Water Balance When the composition is formulated with radioactive sodium 2-pyridinethio1-1-oxide, the zone of inhibition determined as described in Example 5, the gelatin disk exhibits a halo diameter of 54.2 mm. when tested against P. ovale. In the absence of APU resin, a halo diameter of 37.5 m.m. is observed. These results show that APU resin improves the effectiveness of the watersoluble sodium Z-pyridinethiol-l-oxide material as well as the water-insoluble zinc-2-pyridinethiol-l oxide.  
 EXAMPLE 8 Another antimicrobial liquid detergent composition having a pH of 8.2 follows.  
 % by weight Cocoamidopropyl dimethyl betaine 22.4 Sodium N-(2 hydroxyhexadecyl) methyl taurate 6.0 Sodium hexylbenzene sulfonate 0.8 Lauryl dimethyl amine oxide 06 Tribromosalicylanilide 1.0 Resin A 3.0 Water Balance Coco corresponds to the mixture of zilkyls derived from a middle cut of coconut oil. that is, 1% C C 27% C and 7% C When the foregoing composition is formulated with a radioactive (C-l4 tagged) tribromosalicylanilide and the deposition evaluated as described in Example 1, 1.5 micrograms of antibacterial agent are noted on the gelatin disk. As only 0.5 micrograms are deposited in the absence of the APU resin, use of the APU resin increases deposit by 200 percent.  
 EXAMPLE 9 Substitution of 1 percent of trichlorocarbanilide for the tribromosalicylanilide in the composition of Example 8 yields substantially similar results.  
 EXAMPLE 10 A lotion shampoo composition exhibiting effectiveness against P. ovale follows.  
 When the foregoing shampoo having a pH of 8.8 is formulated with radioactive 5,7-diiodo-8- hydroxyquinoline (I-l 25) and the deposition evaluated using the procedure of Example 5, the APU resin results in a 220 percent increase in the deposition of the antimicrobial agent. Improved depositionis also obtained when the pH of the composition to 7.8.  
 When the concentration of 5,7-diiodo-8- 5 hydroxyquinoline is reduced to 1 percent in the composition of Example 10, APU resin achieves a 133 percent increase in deposition of that agent.  
 EXAMPLE 11 The following composition is an improved shampoo composition.  
  by weight Triethanolamine lauryl sulfate 21 Coconut monoethanolamide Triethanolamine 0.7 Sodium chloride 0.8 Methyl cellulose 09 Ethanol 7.0 Resin A 3.0 Fluoroescent agent 1.0 Water Balance When the foregoing composition is formulated with the fluorescent agents listed in Table 111 and a 1.25% concentration thereof is used to contact a l X 1 inch wool swatch for five minutes, the fluorescent values in Table III are obtained on the wool swatch after it is rinsed with five consecutive l0-milliliter portions of water and air dried.  
 The foregoing results show that APU resins improve the brightening effectiveness of fluorescent agents of the anionic type (stilbene disulfonate), nonionic (oxazole) and the cationic type (pyrazoline). The improvement noted in fluorescent varies from 7 to 200 percent.  
 EXAMPLE 12 The following composition is an improved conditioning shampoo.  
  The effectiveness of the aminopolyureylene resin in improving the conditioning properties of the protein is shown by the following procedure. A bleached hair tress about 2.5 inches (weight 0.55 grams) is placed in contact with grams of the shampoo composition of Example 12 and the contact is maintained for 30 minutes. The hair tress is then removed from the shampoo, subjected to five consecutive rinses with 55 milliliters of deionized water each time, air dried, and analyzed spectrophotometrically for hydroxyproline. (Hydroxyproline is an amino acid found in hydrolyzed protein, but not in hair.) The protein and aminopolyureylene resin are soluble in the shampoo composition having a pH of 7.5 and the test results for the composition are set forth in Table IV.  
 Table lV Protein Protein Resin A Deposited (l by weight by weight by weight 1 Hydroxyproline content expressed as protein. The foregoing tabulation shows that aminopolyureylene resin improves the deposition of water-soluble protein onto hair and thereby achieves improved conditioning effects.  
 The foregoing tabulation shows that aminopolyureylene resin improves the deposition of water-soluble protein onto hair and thereby achieves improved conditioning effects.  
  Substitution of a benzophenone ultraviolet absorber or a silicone for the gelatin in Example 12 provides compositions having substantially similar improved effects.  
  When resins having an average molecular weight in the range of 1,000 to 20,000 and a repeating unit of rt g t )t zgg gm p mn-i are substituted for the resin in the composition of Example 12, substantially similar results are obtained.  
 Other compositions exhibiting improved effectiveness because of the presence of an aminopolyureylene by weight C to C alkyl* amidopropyl dimethyl betaine 16.0 resln thereln follow: Triethanolamine lauryl sulfate 4.0 55 Lauryl dimethyl amine oxide 0.5 EXAMPLE l3 Polyoxypropylene-polyoxyethylene block copolymer having a hydrophobic molecular A heavy-duty llquld detergent composition having l of and comammg 20% by improved resistance to color fading because of ultraviweight of polyoxyethylene 5.0 Condensation product of 1:1 mixture of ethylene Olet llght WSZ oxide and propylene oxide on butanol 0 (mol. wt. 4,000 2.0 m Resin A q.s. Sodium tridecylbenzene sulfonate 10.0 Ethanol 1.9 Potassium xylene sulfonate 8.5 Protein q.s. Lauric-myristic diethanolamide 4.5 Water, perfume balance Potassium pyrophosphate 15.0  
 mm) Sodium carboxymethylcellulose 0.5  
  5 2,4 dihydroxybenzophenone 0.05 &#39;Alkyl group corresponds to the mixture of alkyls obtained from middle cut of gyqrogAendted Castor on 8&#39; coconut oil esm Water balance Wilson Protein WSP-X250 obtained by enzymatic hydrolysis of collagen and having an average molecular weight of about 1.000  
 2,2&#39;hydroxy4,4&#39;dimethoxybenzophenone may be substituted for the benzophenone in the composition of Example 13 with substantially similar improved effects.  
 EXAMPLE 14 A built particulate laundry detergent composition exhibiting improved antibacterial effectiveness has the following composition:  
 Fabrics laundered in the foregoing composition exhibit improved antimicrobial effectiveness.  
 EXAMPLE 15 A detergent bar composition exhibiting improved resistance to copper discoloration has the following composition.  
  1 03 cm OH) on; on  
 by weight of an aminopolyureylene resin having a molecular weight in the range of 300 to 100,000 and having the following repeating unit: -(CH ),,(X)(CH ),,NHC(Y)NH- wherein X is NH,  
 5 N-C to C alkyl,  
 Y is O or S and n is 2 or 3; and from 0.05 to 5 percent by weight of an active material which is an antimicrobial agent selected from the group consisting of (A) water-soluble and water-insoluble salts of Z-pyridinethiol-l-oxide; (B) substituted bisphenols having the formula OH OH by weight i I Sodium N lauryl B iminodipropionate 8.75 Sodium C to C alkane sulfonate 24.25 R Sodium tallow soap 26.40 I Sodium tridecylbenzene sulfonate Syrupy phosphoric acid (85%) Stearic Acid n n Eifififfi wherein X is halogen, n is l-3, and R is an alkylene of Water balance 1 to 4 carbon atoms or divalent sulfur; (C) substituted loom salicylanilides having the formula Ethylene thiourea may be substituted for benzotriaz- O O ole in the composition of Example 15 with substantially I g similar results. Y NH&#34; Y While the improved properties appear to be due pri- Z Z marily to enhanced deposition and/or retention of both water-soluble and water-insoluble materials due to the 1 presence of the aminopolyureylene resin in the compowherein Y is hydrogen, halogen or trifluoromethyl and sitions, the actual mechanism is not completely under- Stood Accordingly applicant does not wish to be Z is hydrogen or halogen; (D) substituted carbanilides ,having the following structure bound by any particular scientific theory or explanation.  
  While compositions containing APU resin and an active material may be prepared by admixing resin and active material in any suitable manner, in the preparation of detergent containing compositions, improved effects are obtained when the resin and active material are premixed before admixing with the detergent component.  
  Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that similar results may be obtained when the wherein Y is hydrogen, halogen or trifluoromethyl, W is halogen or ethoxy and W is hydrogen or halogen; (E) mono-higher alkyl quaternary ammonium salts selected from the group consisting of C to C alkyl aminopolyureylene resin is used in combination with a isoquinonnium halides, 8 to 22 alkyl pyridinium wide variety of water-soluble and water-insoluble substances in addition to those specifically described. hdes and Salts having the formula What is claimed is: R0 l. A detergent composition consisting essentially of i i from 2 to 99 percent by weight of a water-soluble or- R I-T- R A- ganic detergent selected from the group consisting of anionic, nonionic, amphoteric, zwitterionic, polar nonionic, and cationic detergents; from 0.05 to 5 percent wherein R is C to C alkyl, R and R are each C to C alkyl, R is C to C alkyl or benzyl, and A is selected from the group consisting of chlorine, bromine, iodine and methosulfate; (F) 5,7-diiodo-8-hydroxyquinoline; (G) l,6-di-(4-chlorophenyldiguanado) hexane and (H) -chloro-2(2,4-dichlorophenoxy) phenol.  
  2. A composition in accordance with claim 1 wherein said resin has an average molecular weight in the range of 1000 to 20,000 and in said repeating unit Y is O and n is 3.  
  3. A composition in accordance with claim 2 wherein said active material is zinc pyridinethiol-l-oxide.  
  4. A composition in accordance with claim 2 wherein said active material is sodium pyridinethiol-l-oxide.  
  5. A composition in accordance with claim 2 wherein said active material is bis(3,5,6-trichloro-2 hydroxyphenyl) methane.  
  6. A composition in accordance with claim 2 wherein said active material is cetyl trimethyl ammonium bromide.  
  7. A composition in accordance with claim 1 wherein said detergent is selected from the group consisting of anionic, amphoteric and zwitterionic detergents and is present in an amount from 10 to 40 percent by weight,  
 said antimicrobial agent is present in an amount from 0.1 to 3 percent by weight, said resin is present in an amount from 0.5 to 3.5 percent by weight, and the balance is primarily water.  
  8. A composition in accordance with claim 1 wherein said detergent is a non-soap anionic or nonionic detergent and is present in an amount of 5 to 20 percent by weight, said antimicrobial agent is present in an amount of 0.1 to 3 percent by weight, said resin is present in an amount of 0.5 to 3.5 percent by weight, and also present is 10 to 25 percent by weight of potassium pyrophosphate, sodium silicate or sodium nitrilotriacetate and 4 to 12 percent by weight of sodium or potassium xylene or toluene sulfonate, with the balance being primarily water.  
  9. A composition in accordance with claim 1 wherein said detergent is a non-soap anionic or nonionic detergent and is present in an amount of about 8 to 40 percent by weight, said antimicrobial agent is present in an amount of about 0.1 to 3 percent by weight, said resin is present in an amount of 0.5 to 3.5 percent by weight, and the balance is a water-soluble inorganic or organic builder salt.