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Publication numberUS3723325 A
Publication typeGrant
Publication dateMar 27, 1973
Filing dateMar 11, 1971
Priority dateSep 27, 1967
Publication numberUS 3723325 A, US 3723325A, US-A-3723325, US3723325 A, US3723325A
InventorsJ Parran
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent compositions containing particle deposition enhancing agents
US 3723325 A
Abstract  available in
Images(10)
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Claims  available in
Description  (OCR text may contain errors)

United States Patent i 3,723,325 DETERGENT COMPOSITIONS CONTAINING PARTICLE DEPOSITION ENHANCING AGENTS John J. Parran, .Ir., Springfield Township, Hamilton County, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Original application Sept. 27, 1967, Ser. No. 671,117, now Patent No. 3,580,583. Divided and this application Mar. 11, 1971, Ser. No. 123,456

Int. Cl. C11d 3/48, 1/38 US. Cl. 252-106 5 Claims ABSTRACT OF THE DISCLOSURE Detergent compositions containing water-insoluble particulate substances, such as antimicrobial agents, and certain cationic polymers which serve to enhance the deposition and retention of such particulate substances on surfaces washed With the detergent composition.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is related to the earlier-filed copending application of John I. Parran, Ir., Ser. No. 476,175, filed July 30, 1965, now abandoned, and is a divisional application of applicants copending application Ser. No. 671,117, filed Sept. 27, 1967, now Patent No. 3,580,853.

BACKGROUND OF THE INVENTION The field of this invention is detergent compositions including shampoos (liquid and cream), laundering, hard surface and dishwashing detergents (granular and liquid), and personal use toilet detergent bars.

Various water-insoluble particulate substances have been incorporated in detergent products for the purpose of imparting some residual property or characterictic on surfaces washed with the products. For example, shampoo compositions containing particulate antidandruif agents have been developed which function by deposition and retention of the particulate agent on the hair and scalp during shampooing. Sufficient quantities of the deposited particulate agents are retained after rinsing to impart some degree of residual antimicrobial activity to the washed hair and scalp. Such antidandrufii shampoo compositions are disclosed, for example, by Karsten, Taylor and Parran in US. Patent 3,236,733, granted Feb. 22, 1966.

Particulate antimicrobial substances have also been used in various laundry detergents and personal use toilet detergent bars to impart residual antimicrobial activity on the fabrics or skin surfaces washed with same. Such products are disclosed by Keller and Jordan in US. Patents 3,134,711, granted May 26, 1964, and 3,256,200, granted June 14, 1966.

Various other water-insoluble or sparingly soluble particulate materials such as sunscreens, fabric brighteners, the whiteners have been employed in detergent compositions and depend for their activity or particle deposition and retention on washed surfaces.

It is apparent that an effective detergent composition, properly used, will by its very nature tend to minimize retention of particulate matter on washed surfaces. Thus, only a relatively small proportion of particles present in such detergent compositions are actually retained after 3,723,325 Patented Mar. 27, 1973 ICC? rinsing of the washed surface. Since the activity of antimicrobial and other particulate agents is in part a function of the quantity of particles deposited and retained on the involved surfaces, measures which enhance deposition and/ or promote retention of such particles serve to reduce the quantity of the substance in the composition required to attain a given level of activity or increase the activity attainable with a given concentration of such particles.

SUMMARY OF THE INVENTION It has now been discovered that water-soluble cationic nitrogen-containing polymers having a molecular Weight within the range from about 2,000 to about 3,000,000, and having a cationic charge density (as defined hereinafter) greater than .001 in aqueous solution, enhance the deposition and retention of water-insoluble or sparingly soluble particulate substances contained in detergent compositions on surfaces washed therewith.

Although the mechanism whereby this phenomenon occurs is not fully understood, it is believed that the polymer coats or attaches itself in some Way on the involved particles imparting a net positive charge thereto which increases the afiinity of the particle for the generally negatively charged washed surfaces.

It is therefore an object of this invention to provide detergent compositions which have improved capacities to impart residual activity or properties to surfaces washed therewith.

It is a further object of this invention to provide improved detergent compositions containing water-insoluble or sparingly soluble particulate substances which are deposited and retained on washed surfaces.

It is yet another object of this invention to provide a method for enhancing the deposition of particulate substances from detergent compositions and the retention of such substances on surfaces washed therewith.

These and other objects will become apparent from the following detailed description of the invention.

DETAILED DESCRIPTION OF THE INVENTION The detergent compositions of this invention are comprised of (1) an organic surface active agent (surfactant, i.e., detergent compound); (2) at least one water-soluble cationic nitrogen-containing polymer having a molecular weight within the range from about 2,000 to about 3,000,- 000 and having a cationic charge density greater than .001 in aqueous solution; and (3) a water-insoluble or sparingly soluble particulate substance capable of imparting a desired residual property to a surface to which it becomes affixed.

In its process aspect, this invention is a method for enhancing the deposition and retention of particulate substances upon surfaces washed with a detergent composition containing same, comprising uniformly admixing said particulate substances with a water-soluble cationic nitrogen-containing polymer having a molecular weight Within the range from about 2,000 to about 3,000,000, and having a cationic charge density greater than .001 in aqueous solution, and incorporating said mixture in a detergent base.

The cationic charge density of a polymer as that term is used herein refers to to the ratio of the number of positive charges on a monomeric unit of which the polynumber of positive charges monomeric unit molecular weight The cationic charge density multiplied by the polymer molecular weight determines the number of positively charged active sites on a given polymer chain.

Organic surfactants which can be used in the compositions of this invention are anionic, ampholytic, polar nonionic, nonionic, zwitterionic or cationic. The surfactant can comprise from about 2% to about 95% by weight of the total composition. Anionic organic surfactants are generally preferred for the purposes of this invention. Suitable anionic surfactants include the water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester radical. Such surfactants include the sodium, potassium, and triethanolamine alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of tallow or coconut oil glycerides; sodium or potassium alkyl benzene sulfonates, especially those of the types described by Gunther et al. in U.S. Pat. 2,477,383, granted July 26, 1949, in which the alkyl group contains from about 9 to about 15 carbon atoms; sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols obtained from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium salts of sulfuric acid esters of the reaction product of one mole of a higher alcohol (i.e., tallow or coconut oil alcohols) and about 3 moles of ethylene oxide; and the water-soluble salts of condensation products of fatty acids with sarcosine, e.g., triethanolamine N-acyl sarcosinate, the acyl radicals being derived from coconut oil fatty acids.

Preferably, anionic organic surfactants of the high sudsing type are used for the shampoo embodiments of this invention. Thus, alkyl glyceryl ether sulfonates, N-acyl sarcosinates, and alkyl ether ethylene oxide sulfates as described above are used to special advantage. These and the foregoing surfactants can be used in the form of their sodium, potassium or lower alkanolamine (e.g., mono-, di-, and triethanolamine) salts.

Conventional soaps are also operable anionic surfactants for the purposes of this invention. Suitable soaps include the Water-soluble salts, e.g., sodium, potassium, and lower alkanolamine salts of fatty acids occurring in coconut oil, soybean oil, castor oil or tallow, or synthetically produced fatty acids may be used.

Polar nonionic surfactants can be used herein, either alone or in admixture with anionic and/or ampholytic surfactants. Surfactants of this class can serve to enhance lathering and cleaning properties of anionic detergents. By polar nonionic surfactant is meant a surfactant in which the hydrophilic group contains a semi-polar bond directly between two atoms, e.g., N O, P O, As O, and S O. (The arrow is the conventional representation of a semi-polar bond.) There is charge separation between the two directly bonded atoms, but the surfactant molecule bears no net charge and does not dissociate into ions.

A preferred polar nonionic surfactant for use in the present compositions is amine oxide of the general formula R R R N O, wherein R is an alkyl, alkenyl, or monohydroxyalkyl radical having from about to 16 carbon atoms, and R and R are each methyl, ethyl, propyl, ethanol or propanol radicals. An especially preferred amine oxide is dodecyldimethylamine oxide.

Other operable polar nonionic surfactants are the phosphine oxides having the general formula R R R P O, 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 or monohydroxyalkyl radicals containing from 1 to 3 carbon atoms. A preferred phosphine oxide is dodecyldimethyl phosphine oxide.

Suitable amphoteric surfactants include the alkyl betaiminodipropionates, RN (C H COOM) alkyl beta-aminopropionates, RN(H)C H COOM; and long chain imidazole derivatives having the general formula:

In each of the above formulae, R is an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms and M is a cation to neutralize the charge of the anion, e.g., alkali metal such as sodium and potassium and ammonium and substituted ammonium cations. Specific operable amphoteric surfactants include the disodium salt of lauroyl-cycloimidinium-l-ethoxyethionic acid-2- ethionic acid, dodecyl beta-alanine, and the inner salt of Z-trimethylamino lauric acid. As zwitterionics, the substituted betaines such as alkyl dimethyl ammonio acetates wherein the alkyl radical contains from about 12 to about 18 carbon atoms can also be used. Several examples of this class of zwitterionic surfactants are set forth in Canadian Pat. 696,355, granted Oct. 20, 1964.

Especially preferred shampoo compositions in accordance with this invention will contain a non-soap anionic organic surfactant at a concentration of from about 8% to about 30% by weight of the total composition.

Although nonionic and cationic surfactants are not preferred for the purposes of this invention they can nevertheless be used without substantial loss of the advantageous effects of the cationic polymers on deposition and retention of particulate matter on washed surfaces. Nonionic surfactants may be described as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. As those skilled in the art are well aware, the length of the hydrophilic or polyoxyalkylene radical required for condensation with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well known class of nonionics is made available on the market under the tradename of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule, of course, exhibits water insolubility. The molecular weight of this portion is of the order of 950 to 4,000. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole. Liquid products are obtained up to the point where polyoxyethylene content is about of the total weight of the condensation product.

Suitable nonionics also include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having about 6 to 12 carbon atoms, either straight chain or branch chain, in the alkyl group with ethylene oxide in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octane, or nonane, for example.

Other suitable nonionics may be derived by the condensation of ethylene oxide With the product resulting from the reaction of propylene ox de and ethylene diamine. Here again, a series of compounds may be produced, depending on the desired balance between hydrophobic and hydrophilic elements. For example, compounds (molecular weight from about 5,000 to about 11,000) of about 40% to 80% polyoxyethylene content and resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.

Further satisfactory nonionics include the condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, either straight chain or branch chain, with ethylene oxide, an example being a coconut alcohol/ethylene oxide condensate having from to moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

Cationic surfactants which can be used in the compositions of this invention include distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, coconut alkyl dimethyl benzyl ammonium chloride, dicoconut alkyl dimethyl ammonium chloride, cetyl pyridimium chloride, and cetyl trimethyl ammonium bromide.

As hereinbefore indicated, the compositions of this invention contain as an essential component a watersoluble cationic nitrogen-containing polymer having a molecular weight within the range from about 2,000 to about 3.000.000 and a cationic charge density greater than .001 in aqueous solution.

Operable cationic polymers for the purpose of this invention include polyethylenimine or alrkoxylated polyethylenimine polymers. It is believed that the structural formula of the backbone of polyethylenimine is:

wherein x represents a whole number of sufficient magnitude to yield a polymer of molecular weight greater than about 2,000. Branch chains occur along the polymeric backbone and the relative proportions of primary, secondary and tertiary amino groups present in the polymer will vary, depending on the manner of preparation. The distribution of amino groups in a typical polyethylenimine is approximately as follows:

The polyethylenimine is characterized herein in terms of molecular weight. Such polymers can be prepared, for example, by polymerizing ethylenimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods are described in US. Pat. Nos. 2,182,306, Ulrich et al., granted Dec. 5, 1939; 3,033,746, Mayle et al., granted May 8, 1962; 2,208,095, Esselmann et al., granted July 16, 1940; 2,806,839, Crowther, granted Sept. 17, 1957; and 2,553,696, Wilson, granted May 21, 1951. Polyethylenimine has a cationic charge density of .004 in aqueous solution at pH 7.0.

Similarly, alkoxylated polyethylenimine can be pre pared, for example, by reacting one part by weight ethylene oxide or propylene oxide with one part by weight of polyethylenimine prepared as described above and having a molecular weight greater than about 2,000. Preferably, the weight ratio of polyethylenimine to alkylene oxide is at least about 1:1. If this ratio is less than about 1:1 the cationic charge density of the polymer in aqueous solution will not be greater than .001 as is required for the purpose of this invention. A preferred ethoxylated polyethyleniminehas a molecular weight of about 80,000 to 120,000 and a cationic charge density of .004 in aqueous solution at pH 7.0.

Yet another class of water-soluble cationic nitrogencontaining polymers which can be used in the practice of this invention are those in which at least 30 mole percent of the molecular structure is composed of monomeric units containing one or more quaternary ammonium groups and any balance of which is comprised of non quaternized polymeric units derived from monoethylenically unsaturated monomeric groups. The degree of quaternization must be sufficient to provide a cationic charge density greater than about .001. Such polymers include, for example, quaternized polyvinylimidazole, quaternized poly(dimethylaminoethylmethacrylate), quaternized (poly(diethylaminoethylmethacrylate), quaternized (poly(p-dimethylaminomethylstyrene) and others disclosed by Lang in US. Pat. 3,313,734, granted Apr. 11, 1967, all having molecular weights within the range from about 2,000 to 3,000,000.

Still other types of water-soluble cationic polymers us..- ful herein are the following:

1) Water-soluble quaternary nitrogen-substituted cellulose ether derivatives, such as the polymer formed by reacting a hydroxyethylcellulose (having a degree of substitution with hydroxyethyl groups of 1.3) with the reaction product of 0.7 mole of epichlorohydrin and 0.7 mole of trimethylamine, per substituted anhydroglucose unit thereof, said polymer having a cationic charge density of .002 and a molecular weight within the range from about 200,000 to 230,000. This polymer has the structural formula Hydroxyethylcellulose is, of course, comprised of hydroxyethyl-substituted anhydroglucose units with varying degrees of hydroxyethyl substitution. This material is preared by reacting alkaline cellulose with ethylene oxide as is more fully described by Gloor et al., Ind. Eng. Chem., 42:2150 (1950). The extent of substitution with the quaternary nitrogen-containing group must be s-ufficient to provide a cationic charge density greater than .001, and the molecular weight of the substituted hydroxyethylcellulose polymer must be within the range from about 2,000 to 3,000,000.

The preferred cellulose ether derivative from which the quaternary ammonium-substituted polymers described above are prepared include those which are water-soluble nonionic lower alkyl or hydroxyalkyl substituted. Such derivatives include methylcellulose, ethylcellulose, and hydroxyethylcellulose.

A particularly efficacious quaternary ammonium-sub stituted cellulose ether derivative for the purpose of this invention is available from Union Carbide under the code name JR-lL. This polymer has a molecular weight within the range from 100,000 to 1,000,000 and a cationic charge density of .005.

(2) Water-soluble linear polyamines available from The Rohm & Haas Company under the tradename Primafloc 'C-3. This polymer has a molecular weight within the range from about 30,000 to 80,000 and a cationic charge density in aqueous solution at pH 7.0 greater than .001,

*Hydroxyethyleellulose and contains at least 50 mole percent of units of the formula wherein A is a (C C )-alkylene group having at least 2 carbon atoms extending in a chain between the adjoined N atoms, and R and R are each hydrogen or methyl. This and related polymers operable herein as well as a method for their preparation are fully described in US. Pat. 3,288,707, granted Nov. 29, 1966.

(3) The Water-soluble polymers of tetraethylene pentamine and epichlorohydrin commercially available from the Nalco Chemical Company under the tradenames Nalco 600 and Nalcolyte 605. Such polymers have the formula:

L H .l.

wherein x is an integer of sufficient magnitude to yield a polymer having a viscosity at 74 F. of 21 to 42 centipoise. These polymers have a molecular weight within the range from about 2,000 to 3,000,000 and a cationic charge density greater than .001 in aqueous solution at pH 7.0.

(4) Coagulant Aid #225 commercially available from The Calgon Company. This product is a water-soluble nitrogen-containing polymer having a molecular weight within the range from about 3,000 to 3,000,000 and a cationic charge density greater than .001 in aqueous solution at pH 7.0.

(5) Conductive Polymer #261 commercially available from The Calgon Company. This product is a water-soluble nitrogen-containing polymer having a molecule Weight within the range from about 3,000 to 3,000,000 and at cationic charge density greater than .001 in aqueous solution at pH 7.0.

If the molecular weight of the cationic polymers employed herein is less than about 2,000, no substantial enhancement of particle deposition occurs. Best results are obtained with polymers having a molecular weight within the range from about 30,000 to about 1,000,000.

The cationic polymer can be employed herein at a concentration within the range from about 0.1% to about 10.0% by Weight, preferably from about 0.25% to about 4.0% by weight.

Particulate substances which can be used in the detergent compositions of this invention preferably have an average particle diameter within the range from about 0.2 to about 50 microns and include water-insoluble or sparingly soluble antimicrobial agents, sunscreens, fabric brighteners, and various substances which create a favorable skin feel after washing. These particulate substances depend on deposition and retention on washed surfaces to produce their intended effect.

Particule antimicrobial substances, the deposition and retention of which is enhanced by the cationic polymers described herein include, for example, (a) substituted salicylanilides having the general formula:

Y H Y OH OH Xu Xn wherein x is a halogen and n is an integer from 1 to 3, R is an alkylene radical having from 1 to 4 carbon atoms or divalent sulfur; and (d) mixtures of (a), (b), and (c).

The salicylanilides encompassed by (a) above include 3,4,5-tribromosalicylanilide; S-bromosalicyl 3,5 di(trifiuoromethyl)anilide; 5-chlorosalicyl 3,5 di(trifiuoromethyl)anilide; 3,5-dichlorosalicyl 3,4 dichloroanilide; and 5-chlorosalicyl-3-trifiuoromethyl-4-chloranilide. These and other salicylanilides useful herein are disclosed by Bindler and Model in US. Pat. 2,703,332, granted Mar. 1, 1955.

The preferred carbanilides of (b) above include 3,4,4- trichlorocarbanilide; 3-trifiuoromethyl-4,4-dichlorocarbanilide; 3-trifiuoromethyl-3',4,4'-trichlorocarbanilide; 3,3- bis(trifiuoromethyl-4-eth0xy-4'-chlorocarbanilide; and 3, 5-bis(trifiuoromethyl)-4-chlorocarbanilide.

The compounds in (c) above in which R represents an alkyene radical are more fully described in U.,S. Letters Patent 2,5000,077, granted Dec. 26, 1950. The preferred compounds of the general class of (c) above are those which are symmetrical in structural configuration, such as bis(5-chloro-2-hydroxyphenyl) methane, bis(3,5-dichloro- 2-hydroxyphenyl)methane, bis (3,5,6-trichloro-2-hydroxyphenyl)methane, bis(3,5 dichloro-Z-hydroxyphenyl)sulfiide, bis(3,5,6-trichloro-2-hydroxyphenyl)sulfide, and mixtures thereof.

Additional antimicrobial compounds suitable for use in this invention are N-triehloromethylmercapto-4-cyclohexene-l,2,-dicarboximide and N-(l,l,2,2-tetrachloroethylsulfenyl)-cis-A-4-cyclohexene-1,2-dicarboximide.

Preferred antibacterial agents employed herein are salts of Z-pyridinethiol-l-oxide which has the following structural formula in tautomeric form, the sulfur being attached to the number position of the pyridine ring:

1-l1ydroxy-2-pyridlnethlone Heavy metal salts of the above compounds are sparingly soluble and have a high degree of antibacterial activity. Preferred salts include zinc, cadmium, tin and zirconium Z-pyridinethioll-oxide.

Combinations of the above-described antibacterial substances can also be used to advantage. Such combinations are illustrated in US. Pat. 3,281,366, granted Oct. 25, 1966.

These antimicrobial compounds are used in particulate form, with average particle sizes ranging from about 0.2 to about 30 microns. The quantity of antimicrobial agent employed can range from about 0.1 to about 10% and preferably from about 0.5% to about 2.0% by weight.

Preferred antimicrobial detergent composition in accordance with this invention especially adapted to washing hair and scalp are comprised of from about 10% to about 35% by weight of at least one non-soap anionic,

polar nonionic, ampholytic or zwitterionic surfactant;

from about 0.25% to about 2.0% by weight of a watersoluble cationic nitrogen-containing polymer having a cationic charge density greater than about .001 and having an average molecular weight Within the range from about 30,000 to about 1,000,000; from about 0.5% to about 2.0% by Weight of a water-soluble or sparingly soluble antimicrobial substance in particulate form; and the balance substantially water.

Detergent compositions in accordance with this invention can be prepared by methods well known in the art; however, as hereinbefore indicated, it has been found that especially good results are obtained when the cationic polymer and particulate substances are uniformly admixed in an initial step, with the mixture then being added to an aqueous solution or slurry of the surfactant. If the polymeric component and particulate substance are added to the surfactant separately, the degree of deposition and retention enhancement effected by the polymer will be somewhat less.

Each of the aforementioned components can be incorporated in an aqueous vehicle which may, in addition, include such materials as organic solvents, such as ethanol; thickeners, such as carboxymethylcellulose, magnesium-aluminum silicate, hydroxyethylcellulose or methylcellulose; perfumes; sequestering agents, such as tetrasodium ethylenediaminetetraacetate; and opacifiers, such as zinc stearate or magnesium stearate, which are useful in enhancing the appearance or cosmetic properties of the product.

Coconut acyl monoor diethanol amides as suds boosters, and strongly ionizing salts such as sodium chloride and sodium sulfate may be used to advantage.

Toilet detergent or soap bars containing a cationic polymer and particulate substance according to this invention can be based on soap or non-soap synthetic detergents and can also contain a variety of adjuvants to improve product performance or appearance. Examples of such adjuvants includes free fatty acids, or cold cream to improve cosmetic properties, perfumes, inorganic salts to improve bar firmness, insoluble soap to improve bar texture, coloring matter and the like.

In the case of heavy-duty laundering detergents containing the cationic polymers and particulate substances in accordance with this invention, such detergents can be in granular, flake, liquid or tablet form and can contain, in addition to detergent and inorganic or organic builder compounds (such as those disclosed by Diehl in US. Pat. 3,159,581, granted Dec. 1, 1964), minor amounts of adjuvant materials which make the product more effective or more attractive. The following are mentioned by way of example. A tarnish inhibitor such as benzotriazole or ethylenethiourea may also be added in amounts up to about 2%. Fluorescers, perfume and color while not essential in the compositions of the invention, can be added in amounts up to about 1%. An alkaline material or alkali, such as sodium hydroxide or potassium hydroxide, can be added in minor amounts as supplementary pH adjusters when needed. There can also be mentioned as suitable additives, brightening agents, sodium sulfate, and sodium carbonate.

Corrosion inhibitors generally are also added. Soluble silicates are highly effective inhibitors and can be added to certain formulas of this invention at levels of from about 3% to about 8%. Alkali metal, preferably potassium or sodium, silicates having a weight ratio of SiO :M O of from 1.021 to 28:1 can advantageously be used. M in this ratio refers to sodium or potassium. A sodium silicate having a ratio of SiO :Na O of about 1.6:1 to 2.45:1 is especially preferred for economy and effectiveness.

In the embodiment of this invention which provides for a built liquid detergent, a hydrotropic agent at times is found desirable. Suitable hydrotropes are water-soluble alkali metal salts of toluenesulfonate, benzenesulfonate, and xylenesulfonate. The preferred hydrotropes are the potassium or sodium toluenesulfonates. The hydrotrope salt can be added, if desired, at levels of 1% to about 12%. While a hydrotrope will not ordinarily be found necessary, it can be added if so desired, for any reason including the preparation of a product which retains its homogeneity at a low temperature.

The term coconut alkyl as used herein and in the following examples refers to alkyl groups which are derived from the middle cut of coconut alcohol having the following approximate chain length distribution: 2%==C10, 66%=C 23%-=C14, and 9%=C15. Other compounds designated as coconut oil derived are based on unfractionated coconut oil or its fatty acids.

The following examples are illustrative of several detergent compositions of this invention.

Example I A shampoo composition was prepared having the following composition:

Parts by Weight Sodium coconut alkyl glyceryl ether sulfonate (about 23% diglyceryl and the balance substantially monoglyceryl) Sodium tallow alkyl glyceryl ether sulfonate jabout 23% diglyceryl and the balance 'substantially monoglyceryl; the tallow alkyls correspond to those of substantially saturated tallow alcohols and contain approximately 2% C 32% C and 1 Average particle size 2 microns. Molecular weight 40,00060,000.

The zinc pyridinethione and ethoxylated polyethylenimine were uniformly admixed and added to and uniformly mixed with the balance of the components. The resulting product was a stable cream having excellent cosmetic and antidandruif properties. The degree of deposition of zinc pyridinethione from this composition was much greater than the degree of deposition attained with a similarly formulated product which contained no cationic polymer. Residual antimicrobial activity of surfaces washed with this composition is markedly greater as compared to surfaces washed with a control product without polymer.

Compositions identical to the composition of Example I, but containing 5 micron diameter particles of 3,4,4- trichlorocarbanilide; 3,4,S-tribromoalicylanilide; 4,4'-dichloro-3-(trifluoromethyl)carbanilide; and bis(2-hydroxy- 3,5,6-trichlorophenyl)methane, and 6.5 micron particles of N-trichloromethylmercapto 4 cyclohexene-1,2-dicarboximide and N-(1,1,2,2-tetrachlorethylsulfenyl)-cis-A-4- cyclohexene-1,2-dicarboximide, respectively, in place of zinc Z-pyridinethiol-l-oxide are prepared and compared with control compositions containing these same compounds without cationic polymer. The degree of deposition and retention of these compounds in the presence of the cationic polymer is found to be substantially greater than is attached with the control compositions, and a corresponding increase in residual antimicrobial activity is observed on surfaces washed therewith.

1 1 Example II Another antimicrobial detergent formulation in accordance with this invention is formulated as follows:

Parts by 5 Weight Triethanolamine coconut alkyl sulfate 10.0 Coconut alkyl dimethyl amine oxide 10.0 Monoethanol amide of coconut fatty acids 5.0 Ethanol 10.0 Polyethylenimine 1 0.75 Cadmium 2-pyridinethiol-l-oxide (Average particle size 3.0 microns) 0.25 Water, NaOH to adjust to pH 8.5 Balance 1 A water-soluble cationic polymer having a molecular weight Example III A liquid detergent composition suitable for use as an antidandruff shampoo is formulated as follows:

Parts by Weight Triethanolamine coconut alkyl sulfate 20.0 Monoethanol amide of coconut fatty acid 4.5 Magnesium aluminum silicate 0.9 39

Methylcellulose 0.23

Dye 0.008

Perfume 0.8 Zinc Z-pyridinethiol-l oxide 1.0 40

Polyethylenimine /ethylene oxide reaction product (weight ratio 4:1; molecular weight 50,000; cationic charge density .004 in aqueous solution at pH 7.0) 0.5

Water Balance 1 Average particle size 1.5 microns. Molecular weight 10,000.

This composition provides a substantial degree of antidandruff eifect when used in the customary fashion. The degree of deposition and retention of particulate zinc pyridinethione on the hair and scalp after shampooing with this product is substantially greater than is attained with a similar composition Without the polyethylenimine/ethylene oxide reaction product.

Examples IV V VI VII VIII IX X XI Sodium coconut alkyl (ethoxy) a sulfate 20 Sodium lauroyl sarcosinate 25 5 10 Sodium dodecyl benzene sulfonate l0 25 Q-trimethylamine lauric acid 5 5 25 Triethanolamine coconut alkyl monoglyceride sulfonate Polyethylcnimine 2.0 2.5 0. Polyethylenimine propylene oxide reaction product 1.5 Tin 2-pyridinethiol-1-oxide (average particle size 7 microns) 1.0 0.5 Zirconium 2-pyridinethiol-1- oxide (average particle size microns) 1.0

Balance Molecular weight 10,000; cationic charge density .004 in aqueous solution at pH 7.0.

7 Weight ratio 2:1; molecular weight 30,000; cationic charge density greater than .001 in aqueous solution at pH 7.0.

Each of the above compositions impart a residual antimicrobial activity to surfaces washed therein which is substantially greater than is attainable with similar compositions without the polymeric component.

In Example XI, distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, or dicoconut alkyl dimethyl ammonium chloride can be used in place of sodium dodecyl benzene sulfonate without loss of the improved deposition and retention of zirconium Z-pyridinethiol-l-oxide particles effected by the polyethylenimine.

In Example IV, sodium coconut alkyl (ethoxy) sulfate can be replaced with the condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol and having a molecular weight of 1600 or the condensation product of octyl phenol and ethylene oxide using a mole ratio of 1:15, with substantially equivalent results.

The enhanced deposition and retention of pyridinethione salts was demonstrated as follows: A control composition was formulated as in Example I, but omitting the polyethylenimine/ethylene oxide reaction product. A composition similar in formulation but containing 0.5% of polyethylenimine having a cationic charge density of .004 in aqueous solution at pH 7.0 and a molecular weight of 50,000 was prepared and designated test composition A. A test composition designated B which differed from the control composition in containing 0.5% of the polyethylenimine of composition A and 1.0% of zinc Z-pyridinethiol-l-oxide having an average particle size of 2 microns, rather than 2.0% of this latter component as in the control composition, was also prepared.

The hair of 16 female subjects was shampooed by experienced beauty shop operators who washed half of the hair and scalp of each subject with the control composition. The other half of the subjects hair and scalp was washed in the assigned test composition. The test and control composition were used ad libitum, in quantities sufiicient to provide a good lather. After lathering for 45 seconds, the hair was rinsed and the compositions were reapplied, lathered for 45 seconds and rinsed again. The hair was then dried. A sample of cornified epithelium from both the control and test halves of each subjects scalp was obtained by applying cellulose adhesive tape against the scalp. The tape was then placed on a glass slide with the adhesive in contact with the glass. The slide was examined with a polarizing microscope at approximately 400 diameters with polaroids crossed. While the cornified epithelium exhibited some degree of birefringence the highly anisotropic properties of the particulate zinc Z-pyridinethiol-l-oxide made it readily visible under such viewing conditions. The relative quantity of particulate zinc Z-pyridinethiol-l-oxide was then graded on a 0 to 4 scale, with a grade of 4 indicating heavy deposition, and 0 indicating substantially no deposition.

The following results were obtained.

TABLE 1 Composition: Average degree of deposition Control 2.3 A i 3.4 B 2.6

It can be seen from the above results that deposition and retention of zinc 2-pyridinethiol-1-oxide was substantially greater from a detergent composition which contained 0.5% of polyethylenimine as compared to the control composition which contained the same amount of zinc Z-pyridinethiol-l-oxide without polymer. Similarly, composition B which contained only l.0% of zinc Z-pyridinethiol-l-oxide yielded a somewhat higher degree of deposition and retention than the control composition which contained twice as much of this salt, but no polymer.

In like manner the relative deposition of zinc 2-pyridine-thiol-l-oxide from a detergent composition containing various concentrations of ethoxylated polyethylen- 13 imine was demonstrated as follows: The following compositions were prepared.

TABLE 2 Parts by weight Composition Control D E Sodium coconut alkyl glyceryl ether sulfonate Sodium tallow alkyl glyceryl ether ullo ate Sodium sulfate Sodium N-lauroyl sarcosinate.. N-coconut acyl sarcosinate Coconut acyl diethanolamidm. Acetylated lanolin Perfume Color Zinc 2-pyrldinethiol-1-oxid particle size 2 microns).. Polyethylenimine/ethylene action product l Water 1 Same as Example I.

. 0 1. 0 Balance Each of the compositions was tested in the manner described supra, using a test composition and control composition on each of the test subjects. The results attained were as follows:

Average degree of deposition It can be seen that the degree of deposition attained with composition C containing only half as much zinc 2- pyridinethiol-l-oxide as the control was yet greater than the control. Composition D, which contains 1.0% polymer and only A as much zinc Z-pyridinethiol-l-oxide as the control, displayed only moderately less deposition than the control. Composition E, which contains 2% polymer and only half as much zinc Z-pyridinethiol-l-oxide as the control, provides somewhat greater deposition than the control. Composition F, containing 2.0% polymer and only A as much zinc 2-pyridinethiol-1-oxide as the control, provides a degree of deposition approximately equal to the control.

The degree of enhancement of particle deposition and retention in the presence of cationic polymer is also demonstrated by the Slide Particle Deposition test conducted as follows:

Dandruff scales are collected from the scalps of afllicted individuals and mounted on glass slides with a clear acrylic adhesive. The dandrufi slides are covered with a clean white polyester/ cotton cloth, wetted with water, and washed with a test detergent composition by brushing the cloth-covered slide with a soft toothbrush and using 20 grams of the detergent composition for 50 strokes. The slides are then rinsed for one minute with cloth in place and then for two minutes with cloth removed. The rinse water used is tap water at 37 C. with a flow rate of 4 liters per minute. The slides are then allowed to dry.

The washed slides are examined microscopically at 400 diameters magnification using cross polarized filters. Deposition is graded on a 0-4 scale, no deposition being given a 0 grade, while maximum expected deposition is given a 4 grade. Grades in between vary approximately linearly with the density of deposited particles. Several areas of each slide are given whole number grades before the average for that slide is taken to the nearest /1 of a deposition grade. In each test three slides for each test material are treated in random order. All grading and washing is done on a blind basis.

Detergent compositions substantially corresponding to the composition of Example I but containing 0.5% by weight of zinc Z-pyridinethiol-l-oxide and 2.0% by weight of various cationic polymers of this invention were tested against a control composition without polymer using the method described above. The following results were obtained.

Deposition Improvement of deposition Polymer Test Control grade EO/PEl 3.08 1.92 1.16 N alcolyte 605. 3. 08 2. 00 1. 08 Primafioc O-3. 3. 08 2. 00 1. 08 Ooagulant aid 2 3 08 2.00 1. 08 Conductive polym 3. 08 1. 75 1. 33 L 8. 08 2. 00 1. 08 PVI 1 3.00 2. 00 1. 00 DMAEMA 2. 42 1. 75 0. 76 DEAEMA 2. 50 1. 75 0. 75

i Ethox'ylated polyathylenimine as in Example I.

1 Polyvinylimidazole substantially completely quaternized with dimethyl sulfate, having a molecular weight of from 5 to 20x10 and a cationic charge density of .009.

I Poly(dimethylaminoethylmethaerylate) substantially completely quaternized with methyl phosphate, having a molecular weight between 1,000 and 5,000,000 and a cationic charge density of .006.

Poly(diethylaminoethylrnethacrylate) substantially completely quaternized with dimethyl sulfate, having a molecular weight within the range from about 1,000 and 5,000,000 and a cationic charge density of .005.

It can be seen that substantial enhancement of particle deposition and retention is effected by the inclusion of representative cationic polymers in detergent formulations containing same.

Example XII An antimicrobial milled toilet detergent bar which also constitutes a preferred embodiment of this invention is prepared in accordance with methods well known in the art and having the following composition:

Parts by weight Sodium alkyl glyceryl ether sulfonate 1 8.0

Potassium alkyl sulfate 20.0 Magnesium soap of 80:20 tallow: coconut fatty acids 16.7

Sodium soap of 80:20 tallow: coconut fatty acids 32.4 Inorganic salts (sodium and potassium chlorides and sulfates) 9.2 3,4',S-tribromosalicylanilide (Average particle size 5 microns) 1.0 Cationic polymer 2.0 Water and miscellaneous 10.7

1 Alkyl groups derived from middle cut of alcohols obtained by catalytic reduction of coconut alcohol which has a chain length distribution of coconut substantially as follows: 2%-C1o, 66%-C1a, 23%-C14, and 9%-C1o.

Quaternary ammonium-substituted hydroxyethylcellulose ether formed by reacting a hydroxyethylcellulose ether (having a degree of substitution with hydroxyethyl groups of 1.3) with the reaction product of 0.7 mole epichlorohydrin and 0.7 mole of trimethylamlne per substituted anhydroglucose unit thereof, said polymer having a cationic charge density of .002 and a molecular weight within the range from about 200,000 to 230.000.

15 chloro-3-(trifiuoromethyl)carbanilide and 3,4,5-tribrornosalicylanilide, respectively, with improved deposition and retention of the antimicrobial particles being attained in each case relative to control compositions without cationic polymer.

Additional toilet detergent bars are prepared as in Example XII each containing one of the following cationic polymers in place of the quaternary ammonium-substituted cellulose ether polymer employed therein:

(1) Nalcolyte 605, as hereinbefore defined.

(2) Coagulant Aid 225, as hereinbefore defined.

(3) Conductive Polymer 261, as hereinbefore defined.

(4) Polyvinylimidazole substantially completely quaternized with dimethyl sulfate, having a molecular weight of 5,000, and a cationic charge density of .009.

(5) Poly(dimethylaminoethylmethacrylate) substantially completely quaternized with methyl phosphate, having a molecular weight of 1,000,000, and a cationic charge density of .006.

(6) Poly(diethylaminoethylmethacrylate) substantially completely quaternized with dimethyl sulfate, having a molecular weight of 300,000, and a cationic charge density of .005.

Each of these toilet detergent bars provides a degree of 3,4,5-tribromosalicylanilide particle deposition and retention on skin washed therewith which is substantially greater than is attained with toilet detergent control bars without such polymers.

Example XIII Antimicrobial granular built laundry detergent product is prepared by conventional means, having the following composition:

Parts by weight Sodium alkyl benzene sulfonate (the alkyl group averaging about 12 carbon atoms and being derived from polypropylene) 17.5 Sodium tripolyphosphate 49.7 Sodium sulfate 13.3 Silicate solids 7.0 3,4,4-trichloroearbanilide (particle size averaging 3 microns) 0.5 Quaternized polyvinylimidazole 1.5

Polyvinylimidazole in which 80% of the vinylimidazole units are quaternized with dimethyl sulfate, having a molecu lar weight of 250,000 and a cationic charge density of .007.

Fabrics laundered in this product retain a substantially greater quantity of 3,4,4-t1ichlorocarbanilide particles than do fabrics washed in a control product formulated as above, but without the cationic polymer.

Each of the foregoing examples describe embodiments of this invention which involve antimicrobial particulate substances. As hereinbefore disclosed, the deposition and retention of other particulate substances are also enhanced by the cationic polymers. The following examples are illustrative of detergent compositions in accordance with this invention containing representative particulate substances which function through deposition and retention on Washed surfaces.

Toilet detergent bars desirably contain a sunscreen or ultraviolet absorber which will deposit on the skin in the course of washing therewith to provide protection against harmful sun rays. Suitable particulate ultraviolet absorbers which can be incorporated in detergent bars for this purpose include, for example, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy 2 carboxybenzophenone, and 2-hydroxy-4-methoxybenzophenone. These materials are insoluble particulate solids which are employed in bar soap formulations in concentrations ranging from about 1% to about 5% by weight.

1 6 Example XIV A toilet soap bar containing an ultraviolet absorber is formulated in accordance with this invention as follows:

Percent by weight Sodium soap of 50:50 tallow:coconut fatty acids 73.19

Coconut fatty acid 7.30 Cold cream 1.10 Inorganic salts (sodium chloride and sulfate and silicate solids) 0.87 Perfume 1.23 2 Hydroxy-4-n-octoxybenzophenone (Particle size 10 microns) 2.50 Cationic polymer 1 3.00 Miscellaneous 0.81

Water 10.00

1 Same as Example XII.

When used in the customary fashion, the toilet soap bar of this example effects a substantially greater degree of deposition and retention of the particulate ultraviolet absorber (2-hydroxy-4-n-octoxybenzophenone) on the washed skin surfaces than does an identical composition without polymer.

Additional toilet soap bars are prepared as above but containing 2-hydroxy-4-methoxy-2'-carboxybenzophenone and 2-hydroxy-4-rnethoxybenzophenone, respectively, in place of 2-hydroxy-4-n-octoxybenzophenone, with substantially equivalent results.

Toilet soap bars formulated in accordance with Example XIV are prepared containing polyvinylimidazole substantially completely quaternized with dimethyl sulfate, having a molecular weight of 200,000 and a cationic charge density of .009; quaternized poly(pdimethylaminomethylstyrene) having a molecular weight of 250,- 000 and a cationic charge density of .006; and JRIL, a quaternary ammonium-substituted cellulose derivative supplied by Union Carbide, having a molecular weight within the range from 100,000 to 1,000,000, and a cationic charge density of .004; respectively, in place of the cationic polymer employed in that example. The resulting products are substantially equivalent to the product of Example XIV in terms of particle deposition and retention.

Other insoluble particulate substances which are desirably incorporated in toilet soap or detergent bars include the so-called skin feel enhancers. Such materials are deposited as particles on the skin in the course of washing and create a favorable skin feel after washing. Such materials include, for example, nicotinic acid, talc and silicones, such as Dow-Corning Silicone F-l57. These materials are desirably incorporated in a toilet bar formula at levels of about 10% by weight.

Example XV A bar soap formulation as set forth in Example XIV is prepared substituting 10.2% by weight of nicotinic acid particles (average particle size 5 microns) for the 2-hydroxy-4-n-octoxybenzophenone and coconut fatty acid. The resulting composition yields a substantially greater degree of deposition and retention of nicotinic acid particles on skin washed with the bar than is attained with a bar similarly formulated but without cationic polymer. Similar results are obtained when Dow-Corning Silicone F-l57 is used in place of nicotinic acid.

Various insoluble fabric whiteners or brighteners, such as fluorescent dyes and bluings, e.g., ultramarine blue, deposit as particles on fabrics washed with laundry detergent products containing same. Such materials can be used in heavy-duty laundry detergent products in concentrations up to about 1% by weight.

17 Example XVI A built liquid detergent formulation containing a particulate bluing material and a cationic polymer in accordance with this invention is formulated as follows:

Percent by weight 3(N,N dimethyl N coconutammonio)-2-hydroxypropane-l-sulfonate 9.00 Tergitol 12- P-12 (condensation product of 12 moles of ethylene oxide and one mole of dodecylphenol) 3.00 Tripotassiurn methylene diphosphonate 26.00 Sodium silicate (SiO :Na 0=1.-6:1) i 3.00 Potassium. toluenesulfonate 8.50 Sodium carboxymethylhydroxyethylcellulose 0.30 Ultramarine blue (particle size 1.8 microns) 0.15 Cationic polymer 1 3.5 Water Balance Poly(diethylaminoethylmethacrylate) substantially completely quaternized with dimethyl sulfate, having a molecular weight within the range from about 1,000 and 5,000,000 and a cationic charge density of .005.

The above composition when used to launder white fabrics in the conventional method results in the deposition and retention of substantially greater quantities of the ultramarine blue particles on the washed fabrics than occurs when a product similarly formulated but without cationic polymer is used.

Several additional detergent compositions exemplifying the invention are prepared as follows:

Parts by weight Example XVII XVIII XIX XX Sodium coconut alkyl glyceryl ether sulfonate (about 23% diglyceryl and the balance substantially monoglyceryl) 25. 0 Sodium tallow elkyl glyceryl ether sulfonate (about 23% 'glyceryl and the balance substantially monoglyceryl;

the tallow alkyls correspond to those oi substantially saturated tallow alcohols and contain approximately 2%-Cr4,

3275-010, and 667 -0 3) Sodium chloride Sodium sulfate Sodium N-lauroyl sarcosinate. N-coconut acyl sarcosine Diethanolamide of coconut fatty acids. Aeetylated lanolin Zinc 2-pyridinethiol-1-oxide N-trichloromethylrnereapto-4-cycloh ene-1,2-diearboximide N-(l,1,2,2-tetrachloroethylsulienyl)cis- A4-cyclohexene-1,Z-dicarboximide 8 "i .6

1 Average particle size 2 microns.

9 Average particle size 6.5 microns.

! Average particle size 10.0 microns.

Norm-Polymer 1 in the above example is poly(diethylaminoethyl- Inethacrylate) substantially completely quaternized with dimethylsulfate, having a molecular weight of 2,000,000 and a cationic charge density of .005. Polymer 2 is JR-IL. Polymer 3 is polyethylenimine/ ethylene oxide reaction product (weight ratio 1:1, molecular weight 80 GOO-120,000 and cationic charge density of .004 in aqueous solution at p 7.0. Polymer 4 is Primafloc C-3.

tially greater degree, through the inclusion in said compositions of a cationic polymer as herein defined.

What is claimed is:

1. A detergent composition consisting essentially of:

(I) from about 2% to about of an organic surfactant selected from the group consisting of anionic, ampholytic, polar nonionic, nonionic, and zwitterionic surfactants and cationic surfactants selected from the group consisting of distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, coconutalkyldimethylbenzylammonium chloride, dicoconutalkyldimethylammonium chloride, cetylpyridinium chloride, and cetyltrimeth'ylamrnonium bromide;

(II) from about 0.25% to about 4% of a water-soluble cationic polymer having a molecular weight within the range from about 2,000 to about 3,000,000 and a cationic charge density greater than .001, said polymer being formed from tetraethylene pentamine and epichlorohydrin having the structure:

wherein x is an integer of sufficient magnitude to yield a polymer having a viscosity at 74 F. of 21 to 42 centipoises;

(III) from about 0.1% to about 10% of a waterinsoluble or sparingly soluble particulate substance having an average diameter within the range from 0.2 to 30 microns, selected from the group consisting of (A) antimicrobial substances selected from the group consisting of:

(1) substituted salicylanilides having the general formula:

Y OH O Y Q- Q wherein X is hydrogen or halogen, and Y is hydrogen, halogen or trifiuoromethyl; (2) substituted carbanilides having the general structural formula:

Y o I .wherein Y is hydrogen, halogen, or trifiuoromethyl, X is halogen or ethoxy, X is hydrogen or halogen; (3) substituted bisphenols having the general structural formula:

19 phenone, and 2-hydroxy 4 methoxybenzophenone, and (C) ultramarine blue.

2 The composition of claim 1 wherein the particulate substance is an antimicrobial substance.

3. The composition of claim 2 wherein the particulate substance is a heavy metal salt of 2-pyridinethiol-1-oxide whereon said heavy metal salt is selected from the group consisting of zinc, cadmium, tin, and zirconium salts.

4. The composition of claim 3 wherein the heavy metal 10 and acyl sarcosinates, wherein the ac'yl group contains from about 10 to about 18 carbon atoms.

References Cited UNITED STATES PATENTS 3,355,388 11/1967 Karsten 252-107 3,240,721 3 /1966 Fordyce 260-2 3,400,198 9/ 1968 Lang 424-71 3,489,686 1/1970 Parran 252-106 LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R.

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Classifications
U.S. Classification510/382, 510/133, 510/343, 514/188, 510/492, 510/507, 510/475, 510/394, 510/419, 510/121, 510/319, 510/390
International ClassificationA61Q5/02, A61K8/84, C11D3/48, C11D3/37, A61K8/73, A61Q19/10, C11D3/42, C11D9/22, A61K8/81, C11D3/00, A61K8/49
Cooperative ClassificationA61Q5/02, C11D3/48, C11D3/3773, C11D3/42, C11D3/3703, A61K8/8152, A61Q19/10, A61K8/731, C11D3/0036, A61Q5/006, A61K8/4933, A61K8/817, C11D3/3723, A61K8/84, C11D9/225, C11D3/3769, A61K2800/5426
European ClassificationC11D3/48, C11D3/37B9, C11D3/00B7, A61K8/49C6, A61K8/81K4, C11D3/37C8, A61Q19/10, C11D9/22B, C11D3/42, C11D3/37C8F, A61K8/81R, A61K8/73C, A61Q5/02, C11D3/37B, A61K8/84