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US3898186A - Dishwashing compositions containing gel forming gelatin - Google Patents

Dishwashing compositions containing gel forming gelatin Download PDF

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US3898186A
US3898186A US34935673A US3898186A US 3898186 A US3898186 A US 3898186A US 34935673 A US34935673 A US 34935673A US 3898186 A US3898186 A US 3898186A
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alkyl
sulfate
sodium
gelatin
composition
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Robert Mermelstein
Richard W Benson
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Procter and Gamble Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0008Detergent materials characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions; Pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/75Amino oxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/384Animal products

Abstract

Liquid detergent compositions containing gel-forming gelatin, said compositions being especially suitable for use on kitchen utensils. Said compositions minimize filming and spotting of utensil surfaces upon drying. A method for treating kitchen utensil surfaces with aqueous solutions of gel-forming gelatin is also disclosed.

Description

United States Patent 1191 Mermelstein et a1.

1 1 DISHWASHING COMPOSITIONS CONTAINING GEL FORMING GELATIN [75] Inventors: Robert Mermelstein; Richard W. Benson, both of Cincinnati. Ohio [73] Assignee: The Procter & Gamble Company, Cincinnati, Ohio [22] Filed: Apr. 9, 1973 [21] Appl. No.1 349,356

[52] US. Cl. 252/528; 252/89; 252/526; 252/527; 252/545; 252/546; 252/54'7; 252/551; 252/D1G. 14

[ 1 Aug. 5, 1975 3,548,056 12/1970 Eigen et a1 252/117 X 3,707,503 12/1972 Kenny 252/117 3,775,349 11/1973 Turrell et al..... 252/547 3,793,233 2/1974 Rose et a1 252/551 X FORElGN PATENTSQOR APPLICATIONS 1,050,848 12/1966 United Kingdom 252/89 OTHER PUBLICATIONS Fong et 211., Textile Research Journal, Nov. 1953, pp. 769-775. Encyclopedia of Chemical Technology, Gelatin", Vol. 10, 1966, (second edition), pp. 499508.

Primary Exuminerl-lerbert B. Guynn Attorney, Agent, 0) FirmRichard C. Witte; Thomas H. OFlaherty; Julius P. Filcik [5 7 ABSTRACT Liquid detergent compositions containing gel-forming gelatin, said compositions being especially suitable for use on kitchen utensils. Said compositions minimize filming and spotting of utensil surfaces upon drying. A method for treating kitchen utensil surfaces with aqueous solutions of gel-forming gelatin is also disclosed.

11 Claims, N0 Drawings DISHWASHING COMPOSITIONS CONTAINING GEL FORMING GELATIN BACKGROUND OF THE INVENTION The instant invention relates to liquid detergent compositions especially suitable for dishwashing. Such compositions contain a gel-forming gelatin material which modifies the hard surfaces of kitchen utensils in order to minimize filming and spotting upon drying. A method of improving utensil appearance employing an aqueous solution of a gel-forming gelatin is also provided.

Washing of kitchen utensils and tableware either by hand or by machine is, of course, designed to remove deposited food soil and to impart a clean and shiny appearance to the items so washed. Problems in preserving the appearance of the freshly washed utensils arise, however, when kitchen items are washed and perhaps rinsed in water containing dissolved mineral salts. Upon drying, either by hanQwiping, heating or by open air draining, such dissolved mineral salts from the wash and rinse water tend to deposit on the surfaces of the freshly washed articles resulting in unsightly spotting, filming and streaking of the utensil surfaces.

Attempts have been made to minimize the effect of mineral deposition during utensil drying by employing various additives at either the wash or rinsing stage of dishwashing operation, said additives serving to enhance or promote drainage of residual mineralcontaining water from the drying surfaces. Such additives have, for example, included several types of polymeric materials.

There is a continuing need, however, for compositions and methods which can be employed during dishwashing operations to improved the final dry appearance of washed and dried kitchen utensils and articles. If such compositions and methods are intended to be useful for conventional dishwashing soil removal operations, there is a continuing need for a compatible combination of materials which will simultaneously provide the surfactancy, sudsing and mildness attributes of an acceptable dishwashing detergent composition as well as the anti-spotting and anti-filming benefits described above.

Accordingly. it is an object of the present invention to provide liquid dishwashing detergent composition which provide a clean, shiny spotless appearance to the surfaces of kitchen utensils after such utensils have been washed in said compositions and dried.

It is a further object of the present invention to provide aesthetically acceptable liquid detergent compositions for treating surfaces of kitchen utensils as described above, said compositions having the commercially acceptable dishwashing detergent composition attributes of proper surfactantcy, sudsing and mildness.

It is a further object of the present invention to provide a method useful during or after dishwashing for treating surfaces of kitchen utensils to improve the appearance thereof.

It has been surprisingly discovered that by combining a particular non-interfering organic synthetic surfactant system with certain gel-forming gelatin materials having particular essential gelling characteristics and that by further utilizing such gel-forming gelatin materials in aqueous solution, liquid dishwashing detergent compositions and utensil surface treating methods can be realized which attain the above-stated objectives and which are surprisingly superior to similar compositions and processes of the prior art.

SUMMARY OF THE INVENTION The detergent compositions of the instant invention comprise from about 3 to 45% by weight of an organic synthetic surfactant system; from about 0.1 to 5% by weight of a gel-forming gelatin and from about 5 to 95% by weight water. The organic synthetic surfactant system consists of 1 from about 5 to by weight of the surfactant system of water-soluble alkyl sulfates containing from about 12 to 16 carbon atoms 2) from about 5 to by weight of said system of watersoluble alkyl ether sulfates containing from about 12 to 16 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; and 3) from about 5 to 50% by weight of said system of amine oxide surfactants containing one long chain alkyl moiety of from about 10 to 28 carbon atoms and two moieties which can be either alkyl radicals or hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

The gel-forming gelatin of the instant detergent com positions is a Type B gelatin and must have a Bloom strength of from about 50 to 350.

A kitchen utensil surface treating process of the instant invention comprises contacting such utensils with an aqueous solution of the above-described gel-formin g material, and subsequently allowing said utensils to dry. Concentration of such gel-forming material in aqueous solution ranges from about 2 ppm. to ppm.

DETAILED DESCRIPTION OF THE INVENTION The detergent compositions of the instant invention contain three essential components a particular synthetic organic surfactant system; a particular gelforming gelatin and water. Other optional detergent composition materials can be present in preferred embodiments of said compositions. The surface treating process of the instant invention involves utilization of an aqueous solution of gel-forming gelatin. Each of these aspects of the instant invention are discussed in detail as follows:

ORGANIC SYNTHETIC SURFACTANT SYSTEM From about 3% to about 45% by weight of the instant detergent compositions, preferably from about 20% to about 45% by weight, comprises a synthetic organic surfactant system. It has been surprisingly discoveredthat a particular combination of three types of synthetic organic surfactants can be utilized especially effectively in combination with the gel-forming gelatin described hereinafter without interfering with the desired utensil surface modification properties of the gelatin. Such a surfactant system also posseses desirable surfactancy, sudsing and mildness characteristics. The v organic synthetic surfactant components of the instant surfactant system are the alkyl sulfates, the alkyl ether OX process. Examples of suitable alcohols which can be employed in alkyl sulfate manufacture include decyl, lauryl, myristyl, palmityl, and stearyl alcohols and mixtures of fatty alcohols derived by reducing the glyceridesof tallow and coconut oil.

Any water-soluble salt of such sulfated fatty alcohols can be employed. Water-soluble cations include, for example, sodium, potassium, lithium, ammonium, substituted ammonium and substituted amine.

Specific examples of alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmitylalkyl sulfate, potassium myristyl alkyl sulfate, lithium myristyl alkyl sulfate, potassium tallow alkyl sulfate, sodium tallow alkyl sulfate, ammonium tallow alkyl sulfate, triethanolamine tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate, ammonium coconut alkyl sulfate, triethanolamine coconut alkyl sulfate and mixtures thereof. Highly preferred alkyl sulfates are sodium dodecyl sulfate, sodium tallow alkyl sulfate, potassium tallow alkyl sulfate, ammonium tallow alkyl sulfate, triethanolamine tallow alkyl sulfate, potassium coconut alkyl sulfate, sodium coconut alkyl sulfate, ammonium coconut alkyl sulfate and triethanolamine coconut alkyl sulfate.

The alkyl sulfate component of the surfactant system of the instant invention comprises from about to 75% by weight of said surfactant system, preferably from about to 50% by weight of said system.

The second essential component of the surfactant system of the instant invention comprises water-soluble alkyl ether sulfates containing from about 12 to 16 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide in the alkyl ether sulfate molecule. Alkyl ether sulfates are water-soluble salts of sulfated fatty alcohol ethoxylates. Such alkyl ether sulfate surfactants have the general formula RO(C H O),, 80 M wherein R represents an alkyl chain derived from a higher fatty alcohol containing from about 12 to 16 carbon atoms, n represents the number of moles of ethylene oxide within the compound, i.e. a degree of ethoxylation, and varies from 1 to 30 preferably from 3 to 12 and M represents water-solubilizing cation which can be, for example, sodium, potassium, lithium, ammonium, substituted ammonium or substituted amine.

Specific examples of alkyl ether sulfates include so dium tallow alkyl trioxyethylene sulfate, sodium tallow alkyl hexaoxyethylene sulfate, sodium tallow alkyl nonaoxyethylene sulfate, ammonium tallow alkyl nonaoxyethylene sulfate, sodium tallow alkyl dodecaoxyethylene sulfate, potassium tallow alkyl dodecaoxyethylene sulfate, ammonium tallow alkyl dodecaoxyethylene sulfate, sodium dodecyl hcxaoxyethylene sulfate, lithium coconut alkyl hexaoxyethylene sulfate, potassium tetradecyl dodecaoxyethylene sulfate, triethanolamine dodecyl nonaoxyethylene sulfate, and ammonium coconut alkyldodecaoxyethylene sulfate.

caoxyethylene sulfate, potassium .tallow alkyl dodecaoxyethylene sulfate, ammonium tallow alkyl dodecaoxyethylene sulfate and sodium tallow alkyl trioxyethylene sulfate, accmonium coconut alkyl hexaoxyethylene sulfate, triethanolamine coconut alkyl hexaoxyethylene sulfate and treiethanolamine coconut alkyl dodecaoxyethylene sulfate.

The'alkyl ether sulfate component of the surfactant system of the instant invention comprises from about 5 to by weight of said surfactant system, preferably from about 40 to 60% by weight of said system.

The third essential component of the surfactant system of the instant invention comprises water-soluble amine oxide surfactants. Amine oxides have the general formula R,R R N 0 wherein R, is an alkyl group containing from about 10 to 28 carbon atoms, from O to about 2 hydroxy groups and from O to about 5 ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to 18 carbon atoms and O ether linkages; and wherein each of R and R is selected from the group consisting of alkyl and hydroxyalkyl groups containing from 1 to about 3 carbon atoms. Such tertiary amine oxide materials are generally prepared by direct oxidation of the appropriate tertiary amines according to known methods such as, for example, described in German Patent Specification No. 664,425.

Specific examples of amine oxide surfactants include dimethyl dodecyl amine oxide, dimethyl tetradecyl amine oxide, ethyl methyl tetradecyl amine oxide, cetyl dimethyl amine oxide, dimethyl stearyl amine oxide, cetyl ethyl propyl amine oxide, diethyl dodecyl amine oxide, diethyl tetradecyl amine oxide, dipropyl dodecyl amine oxide, bis-(2-hydroxy ethyl) dodecyl amine oxide, bis-(2-hydroxy ethyl )-3-dodecoxyl hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs the above compounds. Preferred amine oxide surfactants include dimethyldodecylamine oxide, dimethyltetradecylamine oxide, cetyldimethylamine oxide and coconut alkyl dimethylamine oxide.

The amine oxide component of the surfactant system of the instant invention comprises from about 5 to 50% by weight of said surfactant system, preferably from about 10 to 35% by weight of said system.

GEL FORMING GELATIN The second essential component of the compositions of the instant invention is a particular non-toxic gelatin material having a tendency. to form a gel in aqueous solution. Although the scope of the instant invention is not limited by any particular theoretical mechanism, it is believed that the gel-forming-gelatin present in the instantcompositions modifies the surfaces of utensils being washed, said modification serving to promote drainage of wash and rinse water from the drying utensils, thereby reducing spotting and filming. It is possible that a thin layer of gel-forming gelatin is deposited onto utensil surfaces. Such a layer of gelled material facilitates water drainage and imparts a shiny appearance to the utensil surface.

The gel-forming material for utilization in the instant invention is a particular type of gelatin. Gelatin is obtained by selective hydrolysis of collagen, the major intercellular protein constitutent of the white connective tissues of animal skins and bones. It consists of a mixture of water-soluble proteins of high average molecular weight.

Gelatin analyzes, in terms of its elements, 50.5% carbon; 6.8% hydrogen; 17% nitrogen; and 25.21% oxygen. Average molecular weight for the preferred gelatin material of the instant invention ranges from 7000 to 100,000. Gelatin material operable in the instant invention is described in great detail in Gelatin, Encyclopedia of Chemical Technology, Volume 10, John Wiley and Sons, Inc., pages 499-509 and R. H. Bogue, The Chemistry and Technology of Gelatin and Glue, McGraw Hill Book Co., Inc., 1922, both references incorporated herein by reference.

The two general kinds of commercial gelatin manufactured are often designated as Type A (derived from acid-processed collagen) and Type B (from alkalineprocessed collagen). Gelatin obtained by acid treatment (Type A) has an iso-electric point above pH of 7, generally between pH 7 and pH 9, while gelatin obtained by alkaline treatment (Type B) has an isoelectric point between pH 4.6 and pH 5.0. It has been discovered that only the Type B gelatin imparts the required drainage, anti-spotting and anti-filming benefit when utilized in combination with the particular surfactant system of the instant invention.

A most important parameter defining the gelatinforming Type B gelatin of the instant invention is the parameter used to measure the tendency of such gelatin to gel. Gelling strength and tendency is a function of the extent of hydrolysis or degradation of the particular gelatin material.

Gelling strength or tendency is measured by a parameter known in the art as Bloom strength. Such a parameter is measured by means of a Bloom Gelometer, a device customarily used for measuring the strength of a gelatin gel under standard conditions. The standard testing procedure used to derive this parameter is set forth in detail in numberous references. Among such references are Standard Methods for the Sampling and Testing of Gelatins, Gelatin Manufacturers Institute of America, lnc., 501 Fifth Avenue, Room 1014, New York 17, New York., and Standard Methods for Determining Viscosity and Jelly strength of .Glue, Industrial and Engineering Chemistry, Volume 16, No. 3, pages 3 10-315, both references herein incorporated by reference.

It has been discovered that in order to realize the anti-spotting, anti-filming and shine benefits provided by the instant compositions and processes, the Type B gelforming gelatin of the instant invention must have a Bloom strength of from about 50 to 300, preferably from about 225 to 275. Thus, a highly preferred gelatin material for use in the present'compositions and process is a Type B gelatin having a Bloom strength of from 225 to 275. Such a highly preferred material has a molecular weight of from about 15,000 to 60,000.

Detergent compositions of the instant invention contain from about 0.1% to about 5% by weight of the above described gel-forming Type B gelatin, preferably from about 0.5% to about 3% by weight. For carrying out the surface treating process of the instant invention, gel-forming Type B gelatin of the above-specified equivalent Bloom strength should be present in aqueous solution to the extent of from about 2 to 100 ppm, preferably from about 10 to about 60 ppm.

WATER The third essential component of the liquid dishwashing detergent compositions of the instant invention is water. Enough water must be present to dissolve the essential surfactant system and gel-forming gelatin components and to maintain the liquid nature of the instant compositions. The amount of water present naturally depends upon the amount of surfactant, gelatin and optional components present in the instant compositions. Accordingly, water comprises from about 5 to by weight of the instant composition, preferably from about 50 to 74% by weight.

OPTIONAL COMPONENTS In addition to the above-described three essential components, the instant detergent compositions can optionally contain a wide variety of other non-essential materials. Such optional ingredients include additional non-interfering surfactants, builder salts, suds control agents, gel-formation promoters, hydrotropes, stabilizing electrolytes, solvents bleaches, coloring agents and perfume. Some of these optional materials are described as follows:

Additional Non-Interfering Surfactants Certain surfactant materials other than the three essential surfactant types which comprise the particular essential surfactant system described above can be optionally included in the instant liquid detergent compositions. Concentration of such optional surfactants is not critical.

Such optional surfactants must be non-interfering. A non-interfering surfactant is one which does not inhibit, either by virture of its chemical properties in aqueous solution or hard surface modification properties, utensil surface modification or the formation of a gel layer on utensil surfaces in accordance with the instant invention. Certain surfactants such as the alkyl glyceryl ether sulfonates employed in some commercial light duty liquid detergents tend to be interfering surfactants and are therefore not useful in the instant compositions.

Builders Builder materials can be added to the instant compositions in order to promote the cleaning and soil removal efficacy of the surfactants of the instant detergent compositions. Such materials can be, for example, water-soluble salts of phosphates, polyphosphates, phosphonates, carbonates, silicates, polyacetates, and polycarboxylates as well as mono-, diand triethanolamine compounds.

Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates, and hexametaphosphates. The polyphosphonates specifically include, for example, the sodium and potassium salts of ethylene diphosphonic acid, sodium and potassium salts of ethane l-hydroxy-l, ldiphosphonic acid and the sodium and potassium salts of ethane-1,1,Z-triphosphonic acid. Examples of these and other polyphosphonic builder compounds are disclosed in US. Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176 and 3,400,148, incorporated herein by reference.

Specific examples of nonphosphate detergent builder ingredients include the 1) alkali metal, specifically sodium and potassium, carbonates and silicates, 2) the alkali metal, ammonium and substituted ammonium polyacetates and polycarboxylates and 3) the ethanolamines. Specific examples of the polyacetate and polycarboxylate builder salts include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetra-acetic acid, nitrilotriacetic acid, oxydisuccinic acid, mcllitic acid, benzene polycarboxylic acids, and citric acid. Highly preferred specific builder materials include potassium pyrophosphate, sodium tripolyphosphate, sodium carbonate, sodium acetate, sodium silicate, sodium citrate, sodium nitrilotriacetate, sodium mellitate, triethanolamine and mixtures thereof. pyrophosphate,

When employed in detergent compositions containing the surfactant system and gel-forming gelatin of the instant invention, such optional builder materials generally comprise from about 3% to about 50% by weight of the total detergent composition, preferably from about 5 to about by weight.

Suds Promoting Agents Particular suds promoting agents can be added to detergent compositions of the instant invention in order to enhance sudsing performance. Such materials are basically those which provide water hardness in the form of calcium or magnesium ions. Surprisingly, the addition of such suds promoting agents also seems to enhance the shine-imparting and anti-filming and spotting performance of the instant detergent compositions.

Suds promoting agents which operate by providing artificial water hardness include, of course, any watersoluble calcium or magnesium salt. Specific examples of such salts are calcium acetate, calcium chloride, calcium hydroxide, caldium iodide, calcium lactate, calcium nitrate, monobasic calcium phosphate, magnesium acetate, magnesium chloride, magnesium gluconate, magnesium hydroxide, magnesium lactate, magnesium nitrate, monobasic magnesium phosphate, and magnesium sulfate. When such suds promoting agents are employed they are generally present to the extent of from about 0.1 to 5% by weight of the instant detergent compositions.

Gel Formation Promoting Agents It is further been surprisingly discovered that the anti-spotting, anti-filming and shine-imparting effect of the gel-forming gelatin in the instant compositions can be enhanced by utilization of particular materials which tend to promote cross-linking of the gel structure. Such gel formation promoters are selected from the group consisting of l) water-soluble salts of trivalent metals and 2) aldehyes. Examples of suitable trivalent metal salts include ferric chloride, ferric citrate, ferric nitrate, ferric sulfate, aluminum chloride, aluminum citrate, aluminum nitrate, aluminum sulfate, and stannic chloride pentahydrate. Examples of aldehyde gel promoting agents include formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde. When present in the detergent compositions of the instant invention, the above-described gel promoting agents are present to the extent from about 0.1 to 5 by weight of the composition, preferably from about 0.5% to 2 by weight.

Stabilizing Agents Since the detergent compositions of the instant invention exist in liquid form, such compositions can appropriately contain stabilizing agents such as certain hydrotropes and/or electrolytes to promote phase stability. Commonly employed hydrotropes include conventional lower alkylaryl sulfonates such as sodium and potassium toluene sulfonate, xylene sulfonate, benzene sulfonate and cumene sulfonate. Lower alkanol hydrotropes such as methanol, ethanol, propanol and butanol can also be employed as hydrotropes in the instant invention but are not preferred. Electrolyte salts such as potassium chloride can also optionally be added to improve phase stability of the liquid detergent compositions. When employed, the above-described hydrotropes and/or electrolytes generally comprise from about 1 to 40% by weight of the total composition.

COMPOSITION PREPARATION The instant detergent compositions can be formulated merely by admixing the requisite amounts of the essential and optional components together in any order to form a homogeneous liquid.

SURFACE TREATING PROCESS As noted above, utilization in conventional dishwashing manner of the innstant liquid detergent compositions in dilute aqueous solution (ie to the extent from about 0.05 to 2% by weight in aqueous solution) will serve to promote drainage of film-and spot-causing wash and/or rinse water from kitchen utensils and further serves to impart a shiny appearance to the surfaces of said utensils upon drying,

Inasmuch as the presenceof surfactant in the detergent compositions of the instant invention serves only to aid in soil removal during washing of utensils, the essential gel-forming gelatin of the instant invention can be employed (in the form of a rinse aid) in a surface treating process without the prsence of synthetic organic detergent in order to treat utensil hard surfaces when the cleaning action of a surfactant is not required. In such a case, the surface-treating process aspect of the instant invention comprises contacting such utensil surfaces to be treated with an aqueous solution comprising from about 10 to ppm. of the above described non-toxic gel-forming Type B gelatin, and subsequently allowing such surfaces to dry.

The detergent compositions and surface-treating process of the instant invention are illustrated by the following examples:

EXAMPLE I A light duty liquid diswashing detergent composition is prepared having the following formulation:

COMPONENT WT.

Balance EXAMPLE II A light duty liquid dishwashing detergent composition is prepared having the following formulation:

Component Wt.

Surfactant system 30% Sodium coconut alkyl hexaoxyethylene sulfate 53.4%

Sodium coconut alkyl sulfate -33.3% 100% Coconut alkyl dimethyl amine oxide l 3.3% Gelatin-Type B-Bloom 2% strength 250 Magnesium chloride 1% Potassium Toluene Sulfonate 8% Water and minors Balance Such a composition is physically stable and is effective for cleaning dishes and kitchen utensils when utilized in an 0.2% aqueous solution. Utilization of such a composition imparts shine to utensil hard surfaces and minimizes filming and spotting thereof. Such a composition additionally has commercially acceptable sudsing and mildness characteristics.

Substantially similar dishwashing performance is obtained when the sodium coconut alkyl hexaoxyethylene sulfate of the Example ll composition is replaced with an equivalent amount of sodium coconut alkyl dodecaoxylethylene sulfate, potassium coconut alkyl dodecaoxyethylene sulfate, ammonium cocnut alkyl dodecaoxyethylene sulfate, sodium tallow alkyl dodecaoxyethylene sulfate, ammonium tallow alkyl dodecaoxyethylene sulfate, potassium tallow alkyl dodecaoxyethylene sulfate, sodium tallow alkyl trioxyethylene sulfate, ammonium coconut alkyl hexaoxyethylene sulfate, triethanolamine coconut alkyl hexaoxyethylene sulfate or triethanolamine coconut alkyl dodecaoxyethylene sulfate.

Substantially similar dishwashing performance is obtained when the sodium coconut alkyl sulfate of the Example ll composition is replaced with an equivalent amount of sodium tallow alkyl sulfate, potassium tallow alkyl sulfate, ammonium tallow alkyl sulfate, triethanolamine tallow alkyl sulfate, potassium coconut alkyl sulfate, ammonium coconut alkyl sulfate, sodium dodecyl sulfate or triethanolamine coconut alkyl sulfate.

Substantially similar dishwashing performance .is obtained when the coconut alkyl dimethyl amine oxide of the Example [I composition is replaced with an equivalent amount of dimethyldodecylamine oxide, dimethyltetradecyl amine oxide or cetyldimethylamine oxide.

Substantially similar dishwashing performance is obtained when in the above-described Example ll composition, the gelatin is replaced with an equivalent 10 amount of gelatin, Type B of Bloom strength 1'20 or gelatin Type B of Bloom strength 200.

Substantially similar dishwashing performance is ob tained when in the above-described Example ll composition, the magnesium chloride suds promoting agent is replaced with an equivalent amount of calcium acetate, calcium chloride, calcium hydroxide, calcium iodide, calcium lactate, calcium nitrate, monobasic calcium phosphate, magnesium acetate, magnesium gluconate, magnesium hydroxide, magnesium lactate, magnesium nitrate, monobasic magnesium phosphate or magnesium sulfate.

Substantially similar dishwashing performance and product stability are obtained when in the abovedescribed Example ll composition, the potassium toluene sulfonate hydrotrope is replaced with an equivalent amount of potassium xylene sulfonate, potassium benzene sulfonate, potassium cumene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate sodium benzene sulfonate, sodium cumene sulfonate, methanol, ethanol, propanol, n-butanol, or potassium chloride.

EXAMPLE III A light duty liquid dishwashing detergent composition is prepared having the following formulation:

Such a composition is physically stable and is effective for cleaning dishes and kitchen utensils when utilized in an 0.2% aqueous solution. Utilization of such a composition imparts shine and resistance to filming and spotting to utensil hard surfaces. Such a composition possesses commercially acceptable sudsing and mildness characteristics.

Substantially similar dishwashing performancr .-:s obtained when in the above-described Example I composition, the gelatin is replaced with an ecuivalent amount of gelatin, Type B of Bloom strengm 250 or gelatin Type B of Bloom strength 150.

Substantially similar dishwashing performance is realized when in the above-described Example lll composition the potassium pyrophosphate builder salt is re placed with an equivalent amount of sodium tripolyphosphate, sodium carbonate, sodium acetate, sodium silicate, sodium citrate, sodium oxydisuccinate, sodium nitrilotriacetate, sodium mellitate, triethanolamine or mixtures thereof.

Substantially similar dishwashing performance and composition stability are obtained when in the above described Example lll composition, the potassium toluene sulfonate hydrotrope is replaced with an equivalent amount of potassium xylene sulfonate, potassium benzene sulfonate, potassium cumene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, sodium benzene sulfonate, sodium cumene sulfonate, methanol ethanol, propanol, n-butanol or potassium chloride.

Substantially similar dishwashing performance is obtained when in the above-described Example III composition the ferric chloride gel-promoting agent is replaced with an equivalent amount of ferric citrate, ferric nitrate, ferric sulfate, aluminum chloride, aluminum citrate, aluminum nitrate, aluminum sulfate, stannic chloride pentahydrate, formaldehyde, acetaldehyde, propionaldehyde, or butyraldehyde.

SPOTTING AND FILMING TESTS The ability of the detergent compositions of the instant invention to minimize spotting and filming of kitchen utensils washed therein is determined by means of a spotting and filming test. Two aqueous solutions are prepared and are used to wash food-soiled water glasses, knives and glass microscope slides. The first solution is prepared by dissolving to the extent of 0.2% by weight in water of 7 grains/gal. hardness and 115F., the composition of Example II. The second solution is prepared in like manner by dissolving in the same concentration in water of the same hardness and temperature a composition identical of that of the Example II composition but with the gelatin removed.

The food-soiled articles are washed in two gallon dishpans containing the two solutions described above. After washing, the articles are rinsed under a faucet for 15 seconds in water of7 grains/gal. hardness at 1 15F.

The articles washed with the solution of the Example II composition drain noticeably quicker than the articles washed with the gelatin-free solution when drainage is observed side by side. After all the articles are dry, they are graded for degree of spotting and filming. Water glasses and knives washed with the solution of the Example II composition are graded as being noticeably better in appearance with regard to spotting and filming than the glasses and knives washed with the gelatin-free solution.

The microscope slides are greaded with a modified Hunter Colorimeter for haziness by using such an apparatus to compare the slides with a standard clean slide. Microscope slides washed in the solution of the Example II composition are significantly less hazy than the slides washed in the gelatin-free solution.

In an actual use situation, panelists are asked to compare the dishwashing performance of the Example II composition with a composition identical to Example II with the gelatin removed. Panels of 15 women are asked to wash and rinse two soiled sets of tableware, consisting of glasses, steel knives, plastic bowls and procelain plates as they normally would in their kitches using the two dishwashing compositions. Items in both instances are washed and rinsed under conditions similar to those outlined above. Items are then set in a draining rack to dry.

Immediately after washing and rinsing, the panelists are asked to choose the faster draining set of tableware. More than 75 percent of the panelists selected items washed using the Example ll composition as being faster draining than those washed using the gelatin-free composition. After the articles are dry, panelists then grade the final appearance of the tableware. Panelists again prefer the final appearance of the items washed using the formulation of Example lI.

SOLUTIONS OF GEL-FORMING MATERIAL AS RINSE AID The same kinds of food-soiled table articles as described above in the filming and spotting tests are utilized to demonstrate the efficacy of the surface treating process of the'instant invention in a rinse aid situation. The soiled water glasses, knives and glass microscope slides are washed (under conditions described above) in l a 0.2% solution of the composition of Example II and 2) a 0.2% solution of a composition identical to Example il, but with the gelatin removed. After washing and rinsing as above, all the articles are immersed in a dishpan containing a 0.01% 100 ppm) solution of gelatin (Type B, Bloom strength 250). After the articles are dry, they are graded for degree of spotting and filming as in the spotting and filming test above.

Glasses and knives in both sets are graded as being comparable in appearance (with regard to spotting and filming) to the utensils washed in Example M solution in the spotting and filming test above. The microscope slides in both sets of materials average less haze on the Hunter Colorimeter test than the microscope slides washed with the Example Il composition solution in the spotting and filming tests above.

Panels of 15 women are again asked to wash and rinse two soiled sets of tableware consisting of glasses, steel knives, plastic bowls and porcelain plates as they normally would in their kitchens. Both sets of tableware are washed with formulations of the Example [I composition having the gelatin component removed. One set of tableware is then set to dry in a draining rack with no further treatment; the items in the other set are individually immersed in a dishpan containing a 0.01% (100 ppm) solution of gelatin (Type B, Bloom strength 250) in water. After the articles are dry, panelists grade the final appearance of the tableware, and prefer the end result of those items which were immersed in the gelatin solution.

What is claimed is:

l. A liquid dishwashing detergent composition especially adapted for washing and imparting shine to kitchen utensil surfaces, said composition consisting essentially of:

A. from about 3 to 45% by weight of an organic synthetic surfactant system, said system consisting of i. from about 5 to by weight of said surfactant system of water-soluble alkyl sulfates containing from about 12 to l6 carbon atoms;

ii. from about 5 to 60% by weight of said surfactant system of water-soluble alkyl ether sulfates containing from about 12 to 16 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide in the alkyl ether sulfate molecule; and

iii. from about 5 to 50% by weight of said surfactant system of amine oxide surfactants of the formula R,R R -,N 0 wherein R is an alkyl group containing from about 10 to 28 carbon atoms, from zero to about two hydroxy groups and from zero to about five ether linkages, there being at least one moiety of R which is an alkyl group containing from about 10 to about 18 carbon atoms and zero ether linkages, and wherein each R and R is selected from the group consisting of alkyl and hydroxyalkyl groups containing from one to about 3 carbon atoms;

B. from about 0.l to 5% by weight of a gel-forming Type B gelatin having a Bloom strength within the range of fromabout 50 to 300; and

C. from about 5 to by weight of water.

2. A composition in accordance with claim 1 which additionally contains from about 1 to 40% by weight of a stabilizing agent selected from the group consisting of sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, sodium and potassium benzene sulfonate, sodium and potassium cumene sulfonate, methanol, ethanol, propanol, butanol and potassium chloride.

3. A composition in accordance with claim 1 which additionally contains A. from about 0.1 to by weight of a sudspromoting agent selected from the group consisting of water-soluble salts of calcium and magnesium; and

B. from about 1 to 40% by weight of a hydrotrope stabilizing agent selected from the group consisting of sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, sodium and potassium benzene sulfonate and sodium and potassium cumene sulfonate.

4. A composition in accordance with claim 1 wherein A. the surfactant system comprises from about to 45% by weight of said composition,

B. the gel-forming Type B gelatin comprises from about 0.5 to 3% by weight of said composition; and

C. water comprises from about 50 to 75% by weight of said composition.

5. A composition in accordance with claim 4 which additionally contains from about 0.1 to 5 by weight of a suds-promoting agent selected from the group consisting of water-soluble salts of calcium and magnesium.

6. A composition in accordance wtih claim 2 which additionally contains from about 0.1 to 5%v by weight of a gel formation promoting agent selected from the group consisting of ferric chloride, ferric citrate, ferric nitrate, ferric sulfate, aluminum chloride, aluminum citrate, aluminum nitrate, aluminum sulfate, and stannic chloride pentahydrate.

7. A composition in accordance with claim 4 which additionally contains from about 0.1 to 5% by weight of a gel formation promoting agent selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.

8. A composition in accordance with claim 4 wherein A. the alkyl sulfate component of the surfactant system comprises from about 20 to 50% by weight of said surfactant system;

B. the alkyl ether sulfate component of the surfactant system comprises from about 40 to by weight of said surfactant system; and

C. the amine oxide component of the surfactant system comprises from about 10 to 35% by weight of said surfactant system.

9. A composition in accordance with claim 8 which additionally contains from about 3 to 20% by weight of a builder salt selected from the group consisting of potassium pyrophosphate, sodium tripolyphosphate, sodium carbonate, sodium acetate, sodium silicate, sodium citrate, sodium nitrilotriacetate, sodium mellitate, triethanolamine and mixtures thereof.

10. A composition in accordance with claim 8 wherein A. the alkyl sulfate component of the surfactant system is selected from the group consisting of sodium dodecyl sulfate, sodium tallow alkyl sulfate, potassium tallow alkyl sulfate, treithanolamine tallow alkyl sulfate, potassium coconut alkyl sulfate, sodium coconut alkyl sulfate, ammonium coconut alkyl sulfate and triethanolamine coconut alkyl sulfate;

B. the alkyl ether sulfate component of the surfactant system is selected from the group consisting of sodium coconut alkyl hexaoxyethylene sulfate, sodium coconut alkyl dodecaoxyethylene sulfate, potassium coconut alkyl dodecaoxyethylene sulfate, ammonium coconut alkyl dodecaoxyethylene sulfate, sodium tallow alkyl dodecaoxyethylene sulfate, potassium tallow alkyl dodecaoxyethylene sulfate, ammonium tallow alkyl dodecaoxyethylene sulfate, sodium tallow alkyl trioxyethylene sulfate, ammonium coconut alkyl hexaoxyethylene sulfate, triethanolamine coconut alkyl hexaoxyethylene sulfate and triethanolamine coconut alkyl dodecaoxyethylene sulfate; and

C. the amine oxide component of the surfactant system is selected from the group consisting of dimethyldocecyl amine oxide, dimethyltetradecyl amine oxide, cetyldimethyl amine oxide and coconut alkyl dimethyl amine oxide.

11. A composition in accordance with claim 2 wherein the Type B gelatin has a Bloom strength of from about 225 to 275.

Disclaimer 3,898,186.R0be1=t Memwlstez'n and Richard W. Benson, Cincinnati, Ohio.

DISHWASHING COMPOSITIONS CONTAINING GEL FORM- ING GELATIN. Patent dated Aug. 5, 1975. Disclaimer filed Dec. 11, 1975, by the assignee, The Pwoctey- Gamble Company. Hereby enters this disclaimer to claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 of said patent.

[Oyficial Gazette March 23, 1976.]

Claims (10)

  1. 2. A composition in accordance with claim 1 which additionally contains from about 1 to 40% by weight of a stabilizing agent selected from the group consisting of sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, sodium and potassium benzene sulfonate, sodium and potassium cumene sulfonate, methanol, ethanol, propanol, butanol and potassium chloride.
  2. 3. A composition in accordance with claim 1 which additionally contains A. from about 0.1 to 5 % by weight of a sudspromoting agent selected from the group consisting of water-soluble salts of calcium and magnesium; and B. from about 1 to 40% by weight of a hydrotrope stabilizing agent selected from the group consisting of sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, sodium and potassium benzene sulfonate and sodium and potassium cumene sulfonate.
  3. 4. A composition in accordance with claim 1 wherein A. the surfactant system comprises from about 20 to 45% by weight of said composition, B. the gel-forming Type B gelatin comprises from about 0.5 to 3% by weight of said composition; and C. water comprises from about 50 to 75% by weight of said composition.
  4. 5. A composition in accordance with claim 4 which additionally contains from about 0.1 to 5 % by weight of a suds-promoting agent selected from the group consisting of water-soluble salts of calcium and magnesium.
  5. 6. A composition in accordance wtih claim 2 which additionally contains from about 0.1 to 5% by weight of a gel formation promoting agent selected from the group consisting of ferric chloride, ferric citrate, ferric nitrate, ferric sulfate, aluminum chloride, aluminum citrate, aluminum nitrate, aluminum sulfate, and stannic chloride pentahydrate.
  6. 7. A composition in accordance with claim 4 which additionally contains from about 0.1 to 5% by weight of a gel formation promoting agent selected from the group consisting of formaldehyde, acetaldehyde, propionaldehyde, and butyraldehyde.
  7. 8. A composition in accordance with claim 4 wherein A. the alkyl sulfate componenT of the surfactant system comprises from about 20 to 50% by weight of said surfactant system; B. the alkyl ether sulfate component of the surfactant system comprises from about 40 to 60% by weight of said surfactant system; and C. the amine oxide component of the surfactant system comprises from about 10 to 35% by weight of said surfactant system.
  8. 9. A composition in accordance with claim 8 which additionally contains from about 3 to 20% by weight of a builder salt selected from the group consisting of potassium pyrophosphate, sodium tripolyphosphate, sodium carbonate, sodium acetate, sodium silicate, sodium citrate, sodium nitrilotriacetate, sodium mellitate, triethanolamine and mixtures thereof.
  9. 10. A composition in accordance with claim 8 wherein A. the alkyl sulfate component of the surfactant system is selected from the group consisting of sodium dodecyl sulfate, sodium tallow alkyl sulfate, potassium tallow alkyl sulfate, treithanolamine tallow alkyl sulfate, potassium coconut alkyl sulfate, sodium coconut alkyl sulfate, ammonium coconut alkyl sulfate and triethanolamine coconut alkyl sulfate; B. the alkyl ether sulfate component of the surfactant system is selected from the group consisting of sodium coconut alkyl hexaoxyethylene sulfate, sodium coconut alkyl dodecaoxyethylene sulfate, potassium coconut alkyl dodecaoxyethylene sulfate, ammonium coconut alkyl dodecaoxyethylene sulfate, sodium tallow alkyl dodecaoxyethylene sulfate, potassium tallow alkyl dodecaoxyethylene sulfate, ammonium tallow alkyl dodecaoxyethylene sulfate, sodium tallow alkyl trioxyethylene sulfate, ammonium coconut alkyl hexaoxyethylene sulfate, triethanolamine coconut alkyl hexaoxyethylene sulfate and triethanolamine coconut alkyl dodecaoxyethylene sulfate; and C. the amine oxide component of the surfactant system is selected from the group consisting of dimethyldocecyl amine oxide, dimethyltetradecyl amine oxide, cetyldimethyl amine oxide and coconut alkyl dimethyl amine oxide.
  10. 11. A composition in accordance with claim 2 wherein the Type B gelatin has a Bloom strength of from about 225 to 275.
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Cited By (33)

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US3963649A (en) * 1972-09-11 1976-06-15 The Procter & Gamble Company Liquid detergent composition
US4021377A (en) * 1973-09-11 1977-05-03 Miles Laboratories, Inc. Liquid detergent composition
US4076800A (en) * 1975-01-13 1978-02-28 The Procter & Gamble Company Protein-containing detergent compositions for protecting keratinous materials
US4079020A (en) * 1975-11-07 1978-03-14 Lever Brothers Company Cleaning composition
US4111854A (en) * 1974-03-15 1978-09-05 The Procter & Gamble Company General purpose household cleaner
US4144201A (en) * 1976-11-05 1979-03-13 Lever Brothers Company Liquid detergent compositions having improved drain-dry and mildness properties
WO1983003621A1 (en) * 1982-04-15 1983-10-27 American Home Prod Pourable gel dishwasher compositions
US4451385A (en) * 1982-03-15 1984-05-29 Colgate-Palmolive Company Agent for reducing detergent irritation to skin and eyes
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US4554098A (en) * 1982-02-19 1985-11-19 Colgate-Palmolive Company Mild liquid detergent compositions
US4592892A (en) * 1981-11-12 1986-06-03 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Aqueous sterilizing agent for foods or food processing machines and utensils
EP0204472A3 (en) * 1985-05-28 1987-05-13 The Procter & Gamble Company Cleaning compositions
US4737314A (en) * 1985-02-08 1988-04-12 Nippon Shokubai Kagaku Kogyo Co., Ltd. Stabilized alkylene oxide adduct containing lactic acid or a lactate
US4752411A (en) * 1984-05-28 1988-06-21 Cotelle, S.A. Liquid composition for cleaning hard surfaces
US4796646A (en) * 1983-10-28 1989-01-10 L'oreal Composition and process for treating keratinic substances with at least one anionic polymer and at least one quaternized protein
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US5066568A (en) * 1985-08-05 1991-11-19 Hoehst Celanese Corporation Method of developing negative working photographic elements
US5141664A (en) * 1987-12-30 1992-08-25 Lever Brothers Company, A Division Of Conopco, Inc. Clear detergent gel compositions having opaque particles dispersed therein
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US5244652A (en) * 1991-03-22 1993-09-14 E. B. Michaels Research Associates, Inc. Viscous surface active composition
US5298195A (en) * 1992-03-09 1994-03-29 Amway Corporation Liquid dishwashing detergent
US5389676A (en) * 1991-03-22 1995-02-14 E. B. Michaels Research Associates, Inc. Viscous surfactant emulsion compositions
WO1995008611A1 (en) * 1993-09-20 1995-03-30 The Procter & Gamble Company Thickneded aqueous detergent compositions with improved cleaning performance
US5403579A (en) * 1986-02-25 1995-04-04 E. B. Michaels Research Associates, Inc. Process and composition for oral hygiene
US5424010A (en) * 1993-01-06 1995-06-13 Duliba; Edward P. Light duty liquid detergent composition containing 3-methyl-3-methoxy-butanol
US5464563A (en) * 1993-08-25 1995-11-07 Burlington Chemical Co., Inc. Bleaching composition
US5559263A (en) * 1994-11-16 1996-09-24 Tiorco, Inc. Aluminum citrate preparations and methods
US5698505A (en) * 1994-01-25 1997-12-16 The Procter & Gamble Company High sudsing light duty liquid or gel dishwashing detergent compositions containing long chain amine oxide
US6297278B1 (en) 1991-03-22 2001-10-02 Biosyn Inc. (A Pennsylvania Corporation) Method for inactivating sexually transmitted enveloped viruses
US20040176264A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
US8021493B2 (en) * 2007-05-04 2011-09-20 Ecolab Usa Inc. Method of reducing corrosion using a warewashing composition
US20150094253A1 (en) * 2012-04-27 2015-04-02 Basf Se Phthalocyanine particles and the use thereof

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US4599116A (en) * 1984-11-08 1986-07-08 Parker Chemical Company Alkaline cleaning process

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US3548056A (en) * 1966-06-30 1970-12-15 Colgate Palmolive Co Skin protecting composition containing a water - soluble partially degraded protein
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Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3963649A (en) * 1972-09-11 1976-06-15 The Procter & Gamble Company Liquid detergent composition
US4021377A (en) * 1973-09-11 1977-05-03 Miles Laboratories, Inc. Liquid detergent composition
US4111854A (en) * 1974-03-15 1978-09-05 The Procter & Gamble Company General purpose household cleaner
US4087518A (en) * 1975-01-13 1978-05-02 The Procter & Gamble Company Foaming and conditioning protein-containing detergent compositions
US4076800A (en) * 1975-01-13 1978-02-28 The Procter & Gamble Company Protein-containing detergent compositions for protecting keratinous materials
US4079020A (en) * 1975-11-07 1978-03-14 Lever Brothers Company Cleaning composition
US4144201A (en) * 1976-11-05 1979-03-13 Lever Brothers Company Liquid detergent compositions having improved drain-dry and mildness properties
US4592892A (en) * 1981-11-12 1986-06-03 Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo Aqueous sterilizing agent for foods or food processing machines and utensils
US4554098A (en) * 1982-02-19 1985-11-19 Colgate-Palmolive Company Mild liquid detergent compositions
US4451385A (en) * 1982-03-15 1984-05-29 Colgate-Palmolive Company Agent for reducing detergent irritation to skin and eyes
WO1983003621A1 (en) * 1982-04-15 1983-10-27 American Home Prod Pourable gel dishwasher compositions
US4539145A (en) * 1983-09-15 1985-09-03 The Clorox Company Outside window cleaner containing polyvinyl alcohol and amine-containing polymer
US4796646A (en) * 1983-10-28 1989-01-10 L'oreal Composition and process for treating keratinic substances with at least one anionic polymer and at least one quaternized protein
US4752411A (en) * 1984-05-28 1988-06-21 Cotelle, S.A. Liquid composition for cleaning hard surfaces
US4737314A (en) * 1985-02-08 1988-04-12 Nippon Shokubai Kagaku Kogyo Co., Ltd. Stabilized alkylene oxide adduct containing lactic acid or a lactate
EP0204472A3 (en) * 1985-05-28 1987-05-13 The Procter & Gamble Company Cleaning compositions
US5066568A (en) * 1985-08-05 1991-11-19 Hoehst Celanese Corporation Method of developing negative working photographic elements
US5403579A (en) * 1986-02-25 1995-04-04 E. B. Michaels Research Associates, Inc. Process and composition for oral hygiene
US5047167A (en) * 1987-12-30 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Clear viscoelastic detergent gel compositions containing alkyl polyglycosides
US4836948A (en) * 1987-12-30 1989-06-06 Lever Brothers Company Viscoelastic gel detergent compositions
US5160448A (en) * 1987-12-30 1992-11-03 Lever Brothers Company, Division Of Conopco, Inc. Gel detergent compositions containing a clay and a cross-linked polycarboxylic polymer
US5141664A (en) * 1987-12-30 1992-08-25 Lever Brothers Company, A Division Of Conopco, Inc. Clear detergent gel compositions having opaque particles dispersed therein
US5389676A (en) * 1991-03-22 1995-02-14 E. B. Michaels Research Associates, Inc. Viscous surfactant emulsion compositions
US5244652A (en) * 1991-03-22 1993-09-14 E. B. Michaels Research Associates, Inc. Viscous surface active composition
US6297278B1 (en) 1991-03-22 2001-10-02 Biosyn Inc. (A Pennsylvania Corporation) Method for inactivating sexually transmitted enveloped viruses
US5298195A (en) * 1992-03-09 1994-03-29 Amway Corporation Liquid dishwashing detergent
US5443757A (en) * 1992-03-09 1995-08-22 Amway Corporation Liquid dishwashing detergent
US5424010A (en) * 1993-01-06 1995-06-13 Duliba; Edward P. Light duty liquid detergent composition containing 3-methyl-3-methoxy-butanol
US5464563A (en) * 1993-08-25 1995-11-07 Burlington Chemical Co., Inc. Bleaching composition
WO1995008611A1 (en) * 1993-09-20 1995-03-30 The Procter & Gamble Company Thickneded aqueous detergent compositions with improved cleaning performance
US5698505A (en) * 1994-01-25 1997-12-16 The Procter & Gamble Company High sudsing light duty liquid or gel dishwashing detergent compositions containing long chain amine oxide
US5654261A (en) * 1994-11-16 1997-08-05 Tiorco, Inc. Permeability modifying composition for use in oil recovery
US5662168A (en) * 1994-11-16 1997-09-02 Tiorco, Inc. Process for modifying the water permeability of a subterranean formation
US5559263A (en) * 1994-11-16 1996-09-24 Tiorco, Inc. Aluminum citrate preparations and methods
US20040176264A1 (en) * 2002-12-30 2004-09-09 The Procter & Gamble Company Rinse aid composition containing water-soluble metal salt for use in automatic dishwashing for glassware corrosion protection
US8021493B2 (en) * 2007-05-04 2011-09-20 Ecolab Usa Inc. Method of reducing corrosion using a warewashing composition
US8207102B2 (en) * 2007-05-04 2012-06-26 Ecolab Usa Inc. Compositions including hardness ion and threshold agent and methods employing them to reduce corrosion and etch
US20150094253A1 (en) * 2012-04-27 2015-04-02 Basf Se Phthalocyanine particles and the use thereof

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