US3489686A - Detergent compositions containing particle deposition enhancing agents - Google Patents

Detergent compositions containing particle deposition enhancing agents Download PDF

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US3489686A
US3489686A US689349A US3489686DA US3489686A US 3489686 A US3489686 A US 3489686A US 689349 A US689349 A US 689349A US 3489686D A US3489686D A US 3489686DA US 3489686 A US3489686 A US 3489686A
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polyethylenimine
oxide
particulate
detergent
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John J Parran Jr
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • the field of this invention is detergent compositions including shampoos (liquid and cream), laundering, hardsurface and dishwashing detergents (granular and liquid), and personal use toilet detergent bars.
  • 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 Reller and Jordan in US. Patents 3,134,711, granted May 26, 1964, and 3,256,200, granted June 14, 1966.
  • polyethylenimine and alkoxylated polyethylenimine 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.
  • the detergent compositions of this invention are comprised of (1) an organic surface active agent (surfactant, i.e., detergent compound); (2) a water-soluble cationic polymer selected from the group consisting of polyethylenimine and alkoxylated polyethylenimine having a molecular weight within the range from about 2,000 to about 3,000,000 and (3) a waterinsoluble or sparingly soluble particulate substance capable of imparting a desired residual property to a surface to which it becomes afiixed.
  • an organic surface active agent surfactant, i.e., detergent compound
  • a water-soluble cationic polymer selected from the group consisting of polyethylenimine and alkoxylated polyethylenimine having a molecular weight within the range from about 2,000 to about 3,000,000
  • a waterinsoluble or sparingly soluble particulate substance capable of imparting a desired residual property to a surface to which it becomes afiixed.
  • 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 polyethylenimine or alkoxylated polyethylenimine 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 the ratio of the number of positive charges on a monomeric unit of which the polymer is comprised to the molecular weight of said monomeric unit, i.e.,
  • 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.
  • surfactants include the sodium, potassium, and trienthauolamine 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 US.
  • sarcosine e.g., triethanolamine N-acyl sarcosinate
  • anionic organic surfactants of the high sudsing type are used for the shampoo embodiments of this invention.
  • 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.
  • 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.
  • 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 10 to 16 carbon atoms, and R and R are each methyl, ethyl, propyl, ethanol or propanol radials.
  • R is an alkyl, alkenyl, or monohydroxyalkyl radical having from about 10 to 16 carbon atoms, and R and R are each methyl, ethyl, propyl, ethanol or propanol radials.
  • An especially preferred amine oxide is dodecyldimethylamine oxide.
  • 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 t 3 carbon atoms.
  • 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 t 3 carbon atoms.
  • a preferred phosphine oxide is dodecyldimethyl phosphine oxide.
  • Suitable amphoteric surfactants include the alkyl betaiminodipropionates, RN(C H COOM) alkyl beta-aminoproprionates, RN(H)C H COOM; and long chain imidazole derivatives having the general formula:
  • 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 ca ions.
  • alkali metal such as sodium and potassium and ammonium and substituted ammonium ca ions.
  • Specific operable amphoteric surfactants include the disodium salt of lauroyl-cycloimidinium-l-ethoxy-ethionic acid-2- ethionic acid, dodecyl beta-alanine, and the inner salt of Z-trimethylamino lauric acid.
  • the substituted betaines such as alkyl dimethyl ammonia acetates wherein the alkyl radical contains from about 12 to about 18 carbon atoms can also be used.
  • alkyl dimethyl ammonia acetates wherein the alkyl radical contains from about 12 to about 18 carbon atoms
  • this class of zwitterionic surfactants are set forth in Canadian Patent 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.
  • 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 polyoxyaklylene 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.
  • Pluaronic a well known class of nonionics is made available on the market under the trade name of Pluaronic. 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 50% 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.
  • nonionics may be derived by the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.
  • a series of compounds may be produced, depending on the desired balance between hydrophobic and hydrophilic elements.
  • compounds molecular weight from about 5,000 to about 11,000
  • 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.
  • 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 10 to 30 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 chlora ide, dicoconut alkyl dimethyl ammonium chloride, cetyl pyridinium chloride, and cetyl trimethyl ammonium bromide.
  • compositions of this invention contain as an essential component a watersoluble cationic polyethylenimine or alkoxylated polyethylenimine 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 solutlOIl.
  • 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.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods are described in U.S. Patent 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,
  • alkoxylated polyethylenimine can be prepared, 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.
  • the weight ratio of polyethylenimine to alkylene oxide is at least about 1:1. If this ratio is less than about 1:4 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.
  • the ratio of polyethylenimine to alkylene oxide must be equal to or greater than about 1:4.
  • a preferred ethoxylated polyethylenimine has a molecular weight of about 80,000 to 120,000 and a cationic charge density of .004 in aqueous solution at pH 7.0.
  • 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 anti-microbial 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.
  • Particulate antimicrobial substances the deposition and retention of which is enhanced by the cationic polymers described herein include, for example, (a) substituted salicylanilidies having the general formula:
  • 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,S-tribromosalicylanilide; 5 bromosalicyl-3,5-di(trifluoromethyl)anilide; 5-chlorosalicyl 3,5 di(trifluoromethyl)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. Patent 2,703,332, granted Mar. 1, 1955.
  • the preferred cabanilides of (b) above include 3,4,4- trichlorocarbanilide; 3-trifluoromethyl 4,4 dichlorocarbanilide; 3-trifluoromethyl-3',4,4-trichlorocarbanilide; 3,3-bis (trifluoromethyl)-4-ethoxy 4'-chlorocarbanilide; and 3,5 -bis (trifluoromethyl -4-chlorocarb anilide.
  • R represents an alkylene radical
  • the preferred compounds of the general class of (0) above are those which are symmetrical in structural configuration, such as bis 5 -chloro-2-hydroxy phenyl methane, bis (3 ,5 -dichloro 2-hydroxyphenyl) methane, bis 3,5 ,6-trichloro-2-hydroxyphenyl)methane, bis(3,5-dichloro 2 hydroxyphenyl)- sulfide, bis(3,5,6-trichloro-2-hydroxyphenyl)sulfide, and mixtures thereof.
  • Additional antimicrobial compounds suitable for use in this invention are N-trichloromethylmercapto-4-cyclohexene-1,2-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 2 position of the pyridine ring:
  • 2-pyridinethiol-1-oxide 1-hydroxy-2-pyridinethione
  • 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 2-pyridinethiol-1-oxide.
  • 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 compositions 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 polyethylenimine or alkoxylated polyethylenimine 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.
  • aqueous vehicle which may, in addition, include such materials as organic solvents, such as ethanol; thickeners, such as carboxymethylcellulose, magnesiumaluminum 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.
  • organic solvents such as ethanol
  • thickeners such as carboxymethylcellulose, magnesiumaluminum silicate, hydroxyethylcellulose or methylcellulose
  • perfumes such as tetrasodium ethylenediaminetetraacetate
  • 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.
  • adjuvants include 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.
  • 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. Patent 3,159,581, granted Dec. 1, 1964), minor amounts of adjuvant materials which make the product more effective or more attractive.
  • 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%.
  • alkaline material or alkali such as sodium hydroxide or potassium hydroxide
  • supplementary pH adjusters 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 SIOziMgO of from 1.0:1 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 eifectiveness.
  • a hydrotropic agent at times is found desirable.
  • Suitable hydrotropes are water-soluble Sodium coconut alkyl 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.
  • 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% C 66% C 23% C and 9%.
  • C Other compounds designated as coconut oil derived are based on unfractionated coconut oil or its fatty acids.
  • a shampoo composition was prepared having the following composition:
  • 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 antidandruff 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.
  • 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 Z-pyridinethiol-l-oxide (average particle size 3.0 microns) 0.25 Water, NaOH to adjust to pH 8.5
  • a water-soluble cationic polymer having a molecular weight of 50,000 to 100,000, a cationic charge density of .004 in aqueous solution at pH 7.0, and a viscosity of 2.5 centipoise (absolute viscosity) in a 1% by weight aqueous solution measured with an Ostwald viscosimeter at 100 F.
  • a liquid detergent composition suitable for use as an antidandruif shampoo is formulated as follows:
  • 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.
  • This composition provides a substantial degree of antidandrulf effect when used in the customary fashion.
  • the degree of deposiiton and retention of particulate zinc pyridine thione 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.
  • compositions impart a residual antimicrobial activity to surfaces washed therein which is substantially greater than is attainable with similar compositions without the polymeric component.
  • distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, or dicoconut alkyl dimethyl ammonium chloride can be used in place or sodium dodecyl benzene sulfonate without loss of the improved deposition and retention of zirconium 2-pyridinethiol-l-oxide particles effected by the polyethylen- 1m1ne.
  • 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.
  • 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 2-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 suflicient 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.
  • 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 zine 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 2-pyridinethiol-l-oxide as the control, provides somewhat greater deposition than the control.
  • Composition F containing 2.0% polymer and only Mr as much zinc Z-pyridinethiol-l-oxide as the control, provides a degree of deposition approximately equal to the control.
  • the deposition and retention of the particulate antimicrobial agent 3,4,S-tribromosalicylanilide upon skin washed with the above composition is substantially greater than occurs with a control composition without cationic polymer.
  • Toilet detergent bars identical in composition to the bar described above are prepared, replacing the 3,4',5- tribromosalicylanilide with 4 micron particles of the antimicrobial agents 3,4,4 -trichlorocarbanilide; 4,4'- dichloro 3 (trifluoromethyl)carbanilide; bis(2-hydroxy- 3,5,6 trichlorophenyl)methane; and a 1:1 mixture of 4,4 dichloro 3 (trifluoromethyl)carbanilide and 3, 4',5 tribromosalicylanilide, respectively, with improved deposition and retention of the antimicrobial particles being attained in each case relative to control compositions without polyethylenimine.
  • EXAMPLE XIII An antimicrobial granular built laundry detergent product is prepared by conventional means, having the following composition Parts by wt. Sodium alkyl benzene sulfonate (the alkyl group averaging about 12 carbon atoms and being de- 1 See Footnote 2, Example XII.
  • 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-noctoxybenzophenone, 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 con- 13 centrations ranging from about 1% to about by weight.
  • a toilet soap bar containing an ultraviolet absorber is formulated in accordance with this invention as follows: Percent by wt.
  • 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 methoxybenzophenone, respectively, in place of 2-hydroxy-4-n-octoxybenzophenone, with substantially equivalent results.
  • insoluble particulate substances which are desirably incorporated in toilet soap or detergent bars include the so-called skin feel enhancers.
  • 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-157. 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.
  • 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.
  • fluorescent dyes and bluings e.g., ultramarine blue
  • Such materials can be used in heavy-duty laundry detergent products in concentrations up to about 1% by weight.
  • a built liquid detergent formulation containing a particulate bluing material and a cationic polymer in accordance with this invention is formulated as follows:
  • a detergent composition consisting essentially of (1) from about 2.0% to about 95.0% by weight of a Water-soluble organic detergent selected from the group consisting of ampholytic, zwitterionic, anionic and polar nonionic detergents; (2) from about 0.1% to about 10.0% by weight of a water-soluble cationic polymer selected from the group consisting of polyethylenimine and the reaction product of polyethylenimine and ethylene oxide or propylene oxide in a weight ratio greater than about 1:4, said polymer having a molecular weight within the range from about 2,000 to 3,000,000 and a cationic charge density greater than about .001 in aqueous solution at pH 7.0; and (3) from about 0.1% to about 10.0% by weight of a water-insoluble or sparingly soluble particulate member selected from the group consisting of antimicrobial, ultraviolet absorbent and fluorescent bluing substances, said substance having an average particle diameter within the range from about 0.2 to about 50 microns.
  • a Water-soluble organic detergent selected from the group consisting of
  • composition of claim 1 wherein the cationic polymer is polyethylenimine having an average molecular weight within the range from about 10,000 to about 100,000.
  • composition of claim 1 wherein the cationic polymer is a reaction product of polyethylenimine having an average molecular weight greater than about 2,000 and ethylene oxide, said reaction product having an average molecular weight within the range from about 80,000 to about 120,000, the weight ratio of polyethylenimine to ethylene oxide being from about 1:1 to about 4:1.
  • composition of claim 1 wherein the particulate substance is the 2-pyridinethiol-1-oxide salt of a heavy metal selected from the group consisting of zinc, cadmium, tin and zirconium.
  • composition of claim 1 wherein the particulate substance is 3,4,4trichlorocarbanilide.
  • composition of claim 1 wherein the particulate substance is 3,4',S-tribrornosalicylanilide.
  • composition of claim 1 wherein the particulate substance is 4,4'-dichloro-3-(trifluoromethyl)carbanilide.
  • composition of claim 1 wherein the particulate substance is bis(2-hydroxy-3,5,6-trichlorophenyl)methane.
  • a detergent composition consisting essentially of 1) from about 2% to about of a Water-soluble anionic organic detergent; (2) from about 0.25% to about 4.0% of a water-soluble cationic polymer selected from the group consisting of polyethylenimine and the reaction product of polyethylenimine and ethylene oxide or propylene oxide in a weight ratio of from about 1:1 to about 4:1, said polymer having a molecular weight within the range from about 10,000 to about 100,000; and (3) from about 0.1% to about 10.0% of a water-insoluble or sparingly soluble particulate member selected from the group consisting of antimicrobial, ultraviolet absorbent, and fluorescent bluing substances, said particulate substance having an average particle diameter within the range from about 0.2 to 30 microns.
  • composition of claim 9 wherein the particulate substance is an antimicrobial agent selected from the group consisting of zinc 2-pyridinethiol-1-oxide, 3,4,4-

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US4397322A (en) * 1980-04-28 1983-08-09 Joseph Arbaczawski Non-sudsing shampoo and conditioner composition
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US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4557928A (en) * 1982-07-06 1985-12-10 Amway Corporation Anti-dandruff cream rinse conditioner
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US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
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US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
WO2002036725A1 (en) * 2000-11-02 2002-05-10 Unilever N.V. Composition for cleaning hard surfaces
US20030099570A1 (en) * 1999-09-27 2003-05-29 The Procter & Gamble Company Aqueous compositions for treating a surface
US20040127378A1 (en) * 1999-09-27 2004-07-01 Sherry Alan Edward Hard surface cleaning compositions and wipes
US20090312214A1 (en) * 2002-08-14 2009-12-17 Reckitt Benckiser Inc. Disinfecting Compositions Containing a Polymer Complex of Organic Acid
US20110200650A1 (en) * 2010-02-17 2011-08-18 James Robert Schwartz Non-Aerosol Personal Care Compositions Comprising An Anti-Irritation Agent
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WO2013124784A1 (en) 2012-02-20 2013-08-29 Basf Se Enhancing the antimicrobial activity of biocides with polymers
JP2013224335A (ja) * 2007-09-26 2013-10-31 Lanxess Deutschland Gmbh 殺生物性混合物
US8759277B1 (en) 2013-03-08 2014-06-24 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US8759276B2 (en) 2012-11-28 2014-06-24 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
US20140356311A1 (en) * 2008-02-29 2014-12-04 Joachim LEIPOLD Adhesive agent for application on a sanitary object
EP2476314A4 (en) * 2009-09-07 2015-04-29 Lion Corp DISINFECTANT COMPOSITION AND DISINFECTION PROCEDURE
US9029313B2 (en) 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
US9157049B2 (en) 2012-11-28 2015-10-13 Ecolab Usa Inc. Viscoelastic surfactant based cleaning compositions
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US3875071A (en) * 1970-11-16 1975-04-01 Colgate Palmolive Co Antimicrobial detergent composition containing aminopolyureylene resin
US4161581A (en) * 1973-06-11 1979-07-17 Merck & Co., Inc. Poly-[(dialkyl and hydroxy-dialkyl-imino)ethylene halides] and process
US4033895A (en) * 1975-12-24 1977-07-05 Revlon, Inc. Non-irritating shampoo compositions containing stearyl amine oxide
US4838434A (en) * 1979-11-15 1989-06-13 University Of Utah Air sparged hydrocyclone flotation apparatus and methods for separating particles from a particulate suspension
US4397322A (en) * 1980-04-28 1983-08-09 Joseph Arbaczawski Non-sudsing shampoo and conditioner composition
US4470982A (en) * 1980-12-22 1984-09-11 The Procter & Gamble Company Shampoo compositions
US4383028A (en) * 1981-08-03 1983-05-10 Lorin W. Boots Photographic chemistry
US5037818A (en) * 1982-04-30 1991-08-06 Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. Washing composition for the hair
US4557928A (en) * 1982-07-06 1985-12-10 Amway Corporation Anti-dandruff cream rinse conditioner
US4551506A (en) * 1982-12-23 1985-11-05 The Procter & Gamble Company Cationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
US4597898A (en) * 1982-12-23 1986-07-01 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
US4659802A (en) * 1982-12-23 1987-04-21 The Procter & Gamble Company Cationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
US4661288A (en) * 1982-12-23 1987-04-28 The Procter & Gamble Company Zwitterionic compounds having clay soil removal/anti/redeposition properties useful in detergent compositions
US4664848A (en) * 1982-12-23 1987-05-12 The Procter & Gamble Company Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
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US4891160A (en) * 1982-12-23 1990-01-02 The Proctor & Gamble Company Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties
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US4874538A (en) * 1985-10-29 1989-10-17 The Procter & Gamble Company Toilet soap bar compositions containing water soluble polymers
US4837007A (en) * 1985-12-11 1989-06-06 Lever Brothers Company Fluoridating oral cavity
US4997549A (en) * 1989-09-19 1991-03-05 Advanced Processing Technologies, Inc. Air-sparged hydrocyclone separator
WO1993015177A1 (en) * 1992-01-30 1993-08-05 Casco Nobel Ab Cleaning of equipment with respect to amino resins
US5565145A (en) * 1994-05-25 1996-10-15 The Procter & Gamble Company Compositions comprising ethoxylated/propoxylated polyalkyleneamine polymers as soil dispersing agents
EP0841391A1 (en) * 1996-11-07 1998-05-13 The Procter & Gamble Company Perfume compositions
US5955415A (en) * 1997-08-04 1999-09-21 Lever Brothers Company, Division Of Conopco, Inc. Detergent compositions containing polyethyleneimines for enhanced peroxygen bleach stability
US5904735A (en) * 1997-08-04 1999-05-18 Lever Brothers Company Detergent compositions containing polyethyleneimines for enhanced stain removal
US20030099570A1 (en) * 1999-09-27 2003-05-29 The Procter & Gamble Company Aqueous compositions for treating a surface
US20040127378A1 (en) * 1999-09-27 2004-07-01 Sherry Alan Edward Hard surface cleaning compositions and wipes
US6814088B2 (en) 1999-09-27 2004-11-09 The Procter & Gamble Company Aqueous compositions for treating a surface
US20050043203A1 (en) * 1999-09-27 2005-02-24 The Procter & Gamble Company Aqueous compositions for treating a surface
US20050043204A1 (en) * 1999-09-27 2005-02-24 The Procter & Gamble Company Aqueous compositions for treating a surface
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US7470656B2 (en) 1999-09-27 2008-12-30 The Procter & Gamble Company Pre-moistened wipes
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US8349783B2 (en) 2002-08-14 2013-01-08 Reckitt Benckiser Llc Treatment methods using disinfecting compositions containing a polymer complex of organic acid
US8105999B2 (en) * 2002-08-14 2012-01-31 Reckitt Benckiser Inc. Disinfecting compositions containing a polymer complex of organic acid
US20090312214A1 (en) * 2002-08-14 2009-12-17 Reckitt Benckiser Inc. Disinfecting Compositions Containing a Polymer Complex of Organic Acid
US8673835B2 (en) 2002-08-14 2014-03-18 Reckitt Benckiser Llc Treatment methods using disinfecting compositions containing a polymer complex of organic acid
US9237748B2 (en) 2002-08-14 2016-01-19 Reckitt Benckiser Llc Treatment methods using disinfecting compositions containing a polymer complex of organic acid
JP2013224335A (ja) * 2007-09-26 2013-10-31 Lanxess Deutschland Gmbh 殺生物性混合物
US20140356311A1 (en) * 2008-02-29 2014-12-04 Joachim LEIPOLD Adhesive agent for application on a sanitary object
US9783711B2 (en) * 2008-02-29 2017-10-10 Buck-Chemie Gmbh Adhesive agent for application on a sanitary object
EP2476314A4 (en) * 2009-09-07 2015-04-29 Lion Corp DISINFECTANT COMPOSITION AND DISINFECTION PROCEDURE
US20110200650A1 (en) * 2010-02-17 2011-08-18 James Robert Schwartz Non-Aerosol Personal Care Compositions Comprising An Anti-Irritation Agent
US9464261B2 (en) 2010-05-14 2016-10-11 The Sun Products Corporation Polymer-containing cleaning compositions and methods of production and use thereof
WO2013025742A1 (en) 2011-08-15 2013-02-21 The Procter & Gamble Company Detergent compositions containing pyridinol-n-oxide compounds
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US8759276B2 (en) 2012-11-28 2014-06-24 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
US9765284B2 (en) 2012-11-28 2017-09-19 Ecolab Usa Inc. Viscoelastic amphoteric surfactant based cleaning compositions
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US9157049B2 (en) 2012-11-28 2015-10-13 Ecolab Usa Inc. Viscoelastic surfactant based cleaning compositions
US9127238B2 (en) 2012-11-28 2015-09-08 Ecolab Usa Inc. Foam stabilization with polyethyleneimine ethoxylates
US9029313B2 (en) 2012-11-28 2015-05-12 Ecolab Usa Inc. Acidic viscoelastic surfactant based cleaning compositions comprising glutamic acid diacetate
US10100268B2 (en) 2012-11-28 2018-10-16 Ecolab Usa Inc. Acidic viscoelastic surfactant-based cleaning compositions with an alkali metal salt pseudo-linker
US10246665B2 (en) 2012-11-28 2019-04-02 Ecolab Usa Inc. Viscoelastic amphoteric surfactant based cleaning compositions
US10435308B2 (en) 2013-03-08 2019-10-08 Ecolab Usa Inc. Enhanced foam fractionation of oil phase from aqueous/oil mixed phase via increased viscoelasticity
US9102902B2 (en) 2013-03-08 2015-08-11 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US10773973B2 (en) 2013-03-08 2020-09-15 Ecolab Usa Inc. Enhanced foam removal of total suspended solids and multiply charged cations from aqueous or aqueous/oil mixed phase via increased viscoelasticity
US11987505B2 (en) 2013-03-08 2024-05-21 Ecolab Usa Inc. Enhanced foam removal of total suspended solids and multiply charged cations from aqueous or aqueous/oil mixed phase via increased viscoelasticity
US11718540B2 (en) 2013-03-08 2023-08-08 Ecolab Usa Inc. Enhanced foam fractionation of oil phase from aqueous/oil mixed phase via increased viscoelasticity
US8759277B1 (en) 2013-03-08 2014-06-24 Ecolab Usa Inc. Foam stabilization and oily soil removal with associative thickeners
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points
US9968537B2 (en) 2013-09-06 2018-05-15 Jubilant Life Sciences Limited Anti-dandruff compositions and hair care formulations containing zinc pyrithione and quaternary ammonium salt
US10081781B2 (en) 2015-08-21 2018-09-25 Ecolab Usa Inc. Pyrithione preservative system in solid rinse aid products
US11312925B2 (en) 2015-08-21 2022-04-26 Ecolab Usa Inc. Pyrithione preservative system and C1-C12 ethoxylated alcohol in hard surface cleaning products
US11680229B2 (en) 2015-08-21 2023-06-20 Ecolab Usa Inc. Pyrithione preservative system and C1-C12 ethoxylated alcohol in solid rinse aid compositions
US10865363B2 (en) 2015-08-21 2020-12-15 Ecolab Usa Inc. Pyrithione preservative system in solid rinse aid products
US10781403B2 (en) 2015-08-21 2020-09-22 Ecolab Usa Inc. Pyrithione preservative system in solid rinse aid products
WO2024054841A3 (en) * 2022-09-07 2024-04-18 Isp Investments Llc Alkyl polyglucoside based aqueous antimicrobial compositions

Also Published As

Publication number Publication date
NL160608B (nl) 1979-06-15
GB1228060A (fi) 1971-04-15
BE725146A (fi) 1969-06-09
DE1813660A1 (de) 1970-10-01
DE1813660C3 (de) 1979-01-04
DE1813660B2 (de) 1978-05-03
NL160608C (nl) 1979-11-15
FR96567E (fr) 1973-01-29
NL6817719A (fi) 1969-06-13

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