The present invention generally relates to light duty detergent compositions which useful in the cleaning of hard surfaces. More particularly the compositions of the present invention are directed to light duty detergent compositions which are particularly useful in the manual cleaning of dishes and tableware, as well as being useful in the cleaning of other surfaces particularly hard surfaces. Light duty dishwashing detergent compositions provide effective cleaning of dishes and table ware when manually washed typically in a kitchen sink by a consumer. Commercially successful dishwashing detergent compositions usually necessarily exhibit one or more of the following properties: ready the dispersability into a larger volume of water, good cleaning of soiled surfaces, and, good foam height and/or duration.

Such light duty dishwashing detergent compositions are per se known to the art and available in a wide variety of forms as noted above. Notwithstanding this fact, there yet remains a continuing need in the art for further improvements to light duty dishwashing detergent compositions which are particularly useful in cleaning of dishes and table ware, as well as the cleaning of other surfaces as outlined above and later outlined herein. There is a particular need in the art for still further improvements to light duty dishwashing detergent compositions which provide improved performance over other known art compositions.

It is to these objects and yet further objects that the present invention is directed.

In one aspect the present invention provides a light duty dishwashing detergent composition which comprises:

an anionic surfactant constituent, preferably based on one or more sarcosinate compounds;

a nonionic surfactant constituent, preferably based on one or more amine oxide compounds;

an amphoteric surfactant constituent, preferably based on one or more betaine surfactant compounds;

optionally one or more further constituents which are directed to improving one or more aesthetic or functional features of the light duty dishwashing detergent composition, including where necessary, a pH adjusting constituent, such as an acid or alkaline compound, and/or a hydrotrope constituent; and,

water,

such that the final compositions are in the pH range of about pH 7 - 11, further wherein, the total amount of surfactant compounds present in the detergent composition is between about pH 7.5 - 9.5 and still further, wherein:

(i) the total mass of the surfactant compounds present in the light duty dishwashing detergent composition comprise between about 17.5%wt. and about 30%wt, preferably comprise between about 20%wt. and 27%wt, and/or;

(ii) the ratio of the anionic surfactant compounds (%wt.) to the amphoteric surfactant compounds (%wt) is from about 3.5: 1 to about 7: 1, and preferably from about 4.85: 1 to about 5.5: 1, and/or;

(iii) the ratio of the nonionic surfactant compounds (%wt.) to the amphoteric surfactant compounds (%wt) is from about 0.8: 1 to about 4: 1, and preferably from about 1 : 1 to about 4: 1.

In particularly preferred embodiments the light duty dishwashing detergent composition excludes added conventional organic solvents.

In particularly preferred embodiments the light duty dishwashing detergent composition excludes cationic surfactant compounds, particularly water soluble or water dispersible cationic surfactant compounds which provide a germicidal benefit.

The foregoing light duty dishwashing detergent compositions may also include further constituents which are directed to improving one or more aesthetic or functional features thereof, such as preservatives, colorants, fragrances, thickeners, further surfactants, pH buffers, pH adjusting agents, and the like in the minor amounts which are none the less sufficient to improve one or more of the technical characteristics and/or one or more of the consumer attributes of the compositions.

The foregoing compositions are provided either in the form of a pourable viscous liquid, or maybe in the form of a paste or gel, but especially preferably are pourable liquids which are readily dispersible in water.

In a still further embodiment of the invention, the light duty dishwashing detergent composition is used in a process for the manual cleaning of dishes and/or table ware particularly in the cleaning from food stains. The food stains may be dried, or baked on food stains, or may yet be moist. The compositions of the invention may be used in the formation of a dishwashing liquor or bath for the presoaking treatment, as well as for the manual washing of dishes and tableware.

The compositions of the invention necessarily include an anionic surfactant constituent which includes at least one anionic surfactant compound.

Examples of anionic surfactant compounds which may be used in the an anionic surfactant constituent include alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alkyl ether sulfates, alpha-olefm sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl sulfates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkylpolyglycolethersulfates (e.g., containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, alkylpolysaccharide sulfates, alkylpolyglucoside sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof. These anionic surfactants may be provided as salts with one or more organic counterions, e.g, ammonium, or inorganic counteraions, especially as salts of one or more alkaline earth or alkaline earth metals, e.g, sodium.

Further examples of anionic surfactant compounds include water soluble salts or acids of the formula (ROS(¾) _x M or (RS0 ₃ ) _X M wherein R is preferably a C6-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10-C20 alkyl component, more preferably a Ci ₂ - Ci8 alkyl or hydroxyalkyl, and M is H or a mono-, di- or tri-valent cation, e. g., an alkali metal cation (e. g., sodium, potassium, lithium), or ammonium or substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) and x is an integer, preferably 1 to 3, most preferably 1.

Materials sold under the Hostapur and Biosoft trademarks are examples of such anionic surfactants. Still further examples of anionic surfactant compounds useful in the anionic surfactant constituent include alkyl-diphenyl-ethersulphonates and alkyl-carboxylates. Other anionic surfactants can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C6-C20 linear alkylbenzenesulfonates, C6-C22 primary or secondary alkanesulfonates, C6-C24 olefmsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, C6-C24 alkylpolyglycolethersulfates, alkyl ester sulfates such as C 14-16 methyl ester sulfates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated Ci ₂ -Ci ₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH ₂ CH ₂ 0) _k CH ₂ COO ^" M ⁺ wherein R is a C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Examples of the foregoing anionic surfactants are available under the following tradenames: RHODAPON, STEPANOL, HOSTAPUR, SURFINE, SANDOPAN, NEODOX, BIOSOFT, and AVANEL.

A preferred class of anionic surfactant compounds include sarcosinate surfactants which are alkali metal salts of N-alkyl-N-acyl amino acids. These are salts derived from the reaction of (1) N-alkyl substituted amino acids of the formula:

R-i— NH— CH ₂ — COOH

where Ri is a linear or branched chain lower alkyl of from 1 to 4 carbon atoms, especially a methyl, for example, aminoacetic acids such as N-methylaminoacetic acid (i.e. N-methyl glycine or sarcosine), N-ethyl-aminoacetic acid, N-butylaminoacetic acid, etc., with (2) saturated natural or synthetic fatty acids having from 8 to 18 carbon atoms, especially from 10 to 14 carbon atoms, e.g. lauric acid, and the like.

The resultant reaction products are salts which may have the formula:

where M is an alkali metal ion such as sodium, potassium or lithium; Ri is as defined above; and wherein 2 represents a hydrocarbon chain, preferably a saturated hydrocarbon chain, having from 7 to 17 carbon atoms, especially 9 to 13 carbon atoms of the fatty acyl

O

R ₂ — C—

group

Exemplary useful sarcosinate surfactants include cocoyl sarcosinate, lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate and oleoyl sarcosinate, tallow sarcosinate, myristoyl/stearoyl sarcosinates, as well as salts thereof such as sodium lauroyl sarcosinate, sodium cocoyl sarcosinate, and sodium myristoyl sarcosinates. Such sarcosinates are presently commercially available from Croda Inc., and are marketed as CRODASINIC surfactants.

Desirably the anionic surfactant compounds present in the inventive compositions comprise anionic surfactants which necessarily provide good foaming when used, and which is not undesirably irritating to the skin when used in the manual washing of dishwashing, tableware or other hard surfaces.

The light duty dishwashing detergent compositions advantageously comprise between about l%wt. to about 20%wt, preferably 10%wt. to 17%wt. of or one or more anionic surfactant compounds. Particularly preferred anionic surfactant compounds and amounts thereof include those demonstrated in one or more of the Examples.

The compositions of the invention necessarily include a nonionic surfactant constituent which includes at least one nonionic surfactant compound. Virtually all known art nonionic surfactants may be used in the present inventive compositions. Illustrative examples of suitable nonionic surfactants include, inter alia, condensation products of alkylene oxide groups with an organic hydrophobic compound, such as an aliphatic compound or with an alkyl aromatic compound. Many nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may be varied to adjust these properties. Illustrative examples of such nonionic surfactants include the condensation product of one mole of an alkyl phenol having an alkyl group containing from 6 to 12 carbon atoms with from about 5 to 25 moles of an alkylene oxide. Another example of such a nonionic surfactant is the condensation product of one mole of an aliphatic alcohol which may be a primary, secondary or tertiary alcohol having from 6 to 18 carbon atoms with from 1 to about 10 moles of alkylene oxide. Preferred alkylene oxides are ethylene oxides or propylene oxides which may be present singly, or may be both present.

Illustrative examples of nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C6-Ci8 alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. Examples include the Genapol® series of linear alcohol ethoxylates from Clariant Corp., Charlotte, NC. The 26-L series is based on the formula RO(CH2CH20) _n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H2 ₅ to Ci ₆ ¾3 and n represents the number of repeating units and is a number of from 1 to about 12. Further examples of useful nonionic surfactants include secondary C12-C15 alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tergitol® series of nonionic surfactants (ex. Dow Chemical, Midland, MI). Further exemplary nonionic surfactants include linear primary C11-C15 alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tomadol® series of nonionic surfactants (ex. Tomah Industries). Further examples of useful nonionic surfactants include C6-C15 straight chain alcohols ethoxylated with about 1 to 13 moles of ethylene oxide, particularly those which include about 4 to about 7 moles of ethylene oxide.

Further examples of suitable nonionic surfactants for use as the (b) at least one nonionic surfactant include which may be advantageously included in the inventive compositions are alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers. Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C2-C4 alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.

A class of particularly preferred nonionic surfactants are one or more based C6-C15 straight chain alcohols ethoxylated with about 1 to 13 moles of ethylene oxide, particularly those which include about 4 to about 7 moles of ethylene oxide and which are based on C9- Ci5 straight chain alcohols.

Further useful nonionic surfactant compounds useful in the nonionic surfactant constituent include one or more amine oxide compounds. Exemplary useful amine oxide surfactant compounds include:

alkyl di(Ci-C7) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide;

alkyl di(hydroxy C1-C7) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide;

alkylamidopropyl di(Ci-C7) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and

alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12- 16 carbon atoms, and can be straight or branched chain, saturated or unsaturated.

Particularly preferred are alkyl di(Ci-C2) amine oxides in which the alkyl group has about 10- 14, and preferably has 12 carbon atoms, which are preferably saturated. Especially preferred is lauryl dimethyl amine oxide which in preferred embodiments is present to the exclusion of other amine oxides.

In certain particularly preferred embodiments, one or more amine oxide surfactant compounds are necessarily present.

Still further exemplary useful nonionic surfactant compounds include alkanolamide surfactant compounds, as such provide additional cleaning and which also functions as a foam booster which improves the foaming characteristics of the anionic surfactant compound(s) present in the anionic surfactant constituent. Exemplary useful alkanolamides include one or more monoethanol amides, and diethanol amides of fatty acids having an acyl moiety which contains from about 8 to about 18 carbon atoms, and which may be represented in accordance with the formula:

R1— CO— N(H) _m . ₁ (R ₂ OH)3- _m

where Ri represents a saturated or unsaturated aliphatic hydrocarbon radical of from about 7 to 21 carbon atoms, but preferably from about 1 1 to 17 carbon atoms; R ₂ represents a -CH ₂ - or -CH ₂ CH ₂ -, and m is an integer from 1 to 3, but is preferably 1. Preferably, Ri is a saturated or unsaturated aliphatic hydrocarbon radical comprising from about 1 1 to 17 carbon atoms, and m is 1. Specific examples of such compounds include mono-ethanol amine coconut fatty acid amide and diethanol amine dodecyl fatty acid amide. An exemplary useful and particularly preferred fatty acid amides include cocomonoethanol amide or

cocodiethanolamide, which are presently commercially available as MONAMID CMA or MONAMID MDNA (ex. Mona Industries, Paterson NJ). Further exemplary useful alkanolamides which provide such functions include inter alia: cocamide MEA, cocamide DEA, soyamide DEA, lauramide DEA, oleamide MIPA, stearamide MEA, myristamide MEA, lauramide MEA, capramide DEA, ricinoleamide DEA, myristamide DEA, stearamide DEA, oleylamide DEA, tallowamide DEA, lauramide MIPA, tallowamide MEA, isostearamide DEA, isostearamide MEA, and mixtures thereof. Further useful alkanolamide surfactant compounds include alkanolamides, particularly fatty monoalkanolamides and fatty dialkanolamides, including one or more of those marketed under the Ninol® tradename.

The light duty dishwashing detergent compositions advantageously comprise between about l%wt. to about 10%wt, preferably 2%wt. to 8%wt. of or one or more nonionic surfactant compounds. Particularly preferred nonionic surfactant compounds and amounts thereof include those demonstrated in one or more of the Examples.

The compositions of the invention necessarily include an amphoteric surfactant constituent which includes at least one amphoteric surfactant compound. Betaines may be used as an amphoteric surfactant compound and such compounds provide the dual benefits of providing good foaming benefit as well as providing a useful pH buffering effect.

Exemplary useful betaine surfactants include those according to the general formula:

(+) ( ^" )

R— N(R ₁ ) ₂ -R ₂ COO

wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each Ri is an alkyl group containing from 1 to about 3 carbon atoms; and R2 is an alkylene group containing from 1 to about 6 carbon atoms.

Further exemplary useful betaine surfactants include those which may be represented by the general formula:

CH ₃

I

,— N-R ₂ -COO ^"

I

CH ₃

wherein Ri is an alkyl group containing from 8 to 18 carbon atoms, or the amido radical which may be represented by the following general formula:

0 H

1 I

R— C-N— (CH ₂ ) _a - wherein R is an alkyl group having from 8 to 18 carbon atoms, a is an integer having a value of from 1 to 4 inclusive, and R2 is a C1-C4 alkylene group. Examples of preferred betaines are dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and

dodecyldimethylammonium hexanoate.

The light duty dishwashing detergent compositions advantageously comprise between about l%wt. to about 10%wt, preferably 1.5%wt. to 5%wt. of or one or more amphoteric surfactant compounds. Particularly preferred amphoteric surfactant compounds and amounts thereof include those demonstrated in one or more of the Examples.

In preferred embodiments, the total mass of the surfactant compounds present in the light duty dishwashing detergent composition comprise between about 17.5%wt. and about 30%wt, preferably comprise between about 20%wt. and 27%wt. based on the total mass (weight) of the light duty dishwashing detergent composition of which they form a part.

The present inventor has surprisingly found that in accordance with certain preferred embodiments, improved performance characteristics can be achieved when particular mass proportions of the anionic surfactant compound(s) to the amphoteric surfactant compound(s), and/or particular mass proportions of the nonionic surfactant compound(s) to the amphoteric surfactant compound(s) are maintained in the inventive compositions. In preferred embodiments the mass ratio of the anionic surfactant compounds to the amphoteric surfactant compounds present in the compositions is from about 3.5: 1 to about 7: 1, preferably from about 4.85: 1 to about 5.5: 1, still more preferably from about 5: 1 to about 5.5: 1, and in accordance to certain especially preferred embodiments the respective mass ratios are as disclosed in one or more of the Examples. In preferred embodiments, the mass ratio of the nonionic surfactant compounds to the amphoteric surfactant compounds in the compositions is from about 0.8: 1 to about 4: 1, preferably from about 1 : 1 to about 4: 1, still more preferably from about 1 : 1 to about 1 : 1, yet more preferably from about 1.5: 1 to about 1 : 1, and in accordance to certain especially preferred embodiments the respective mass ratios are as disclosed in one or more of the Examples. In certain particularly preferred embodiments the compositions of the invention concurrently exhibit a mass ratio of the anionic surfactant compounds to the amphoteric surfactant compounds, and a mass ratio mass ratio of the nonionic surfactant compounds to the amphoteric surfactant compounds as disclosed immediately above.

According to particularly preferred embodiments, the light duty dishwashing detergent compositions of the invention are essentially free of (comprise less than 0.5%wt, preferably comprise less than 0.2%wt, preferably comprise less than 0.05%wt.) conventional organic solvents. Alternately, not conventional organic solvents are added as a separate constituent to the light duty dishwashing detergent compositions, although minor amounts of conventional organic solvents may be present when included as a carrier or fluid for a further constituent used to form the light duty dishwashing detergent compositions. Such conventional organic solvents include at least partially water-miscible such as alcohols (e.g., low molecular weight alcohols, such as, for example, ethanol, propanol, isopropanol, and the like), glycols (such as, for example, ethylene glycol, propylene glycol, hexylene glycol, and the like), water-miscible ethers (e.g. diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene glycol

monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethylene glycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate), and mixtures thereof. The light duty dishwashing detergent compositions of the invention may optionally comprise one or more further constituents which are directed to improving the aesthetic or functional features of the inventive compositions. Such conventional additives known to the art include but not expressly enumerated here may also be included in the compositions according to the invention. By way of non-limiting example without limitation these may include : chelating agents, colorants, fragrances, thickening agents, hydrotropes, pH adjusting agents, pH buffers and the like. Many of these materials are known to the art, per se, and are described in McCutcheon 's Detergents and Emulsifiers, North American Edition, 1998; Kirk- Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-541 (1997.) Such optional, i.e., non-essential constituents should be selected so to have little or no detrimental effect upon the desirable characteristics of the present invention. When present, the one or more optional constituents present in the inventive compositions do not exceed about 10%wt, preferably do not exceed 8%wt, and most preferably do not exceed 5%wt. of the composition of which they form a part.

Advantageously included constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user. Known coloring agents, such as water soluble or water dispersible dyestuffs or other colorants may be incorporated in the compositions in effective amounts.

The compositions of the invention optionally but in certain cases desirably include a fragrance constituent. Fragrance raw materials may be divided into three main groups: (1) the essential oils and products isolated from these oils; (2) products of animal origin; and (3) synthetic chemicals. Fragrance compositions as received from a supplier may be provided as an aqueous or organically solvated composition, and may include as a hydrotrope or emulsifier a surface-active agent, typically a surfactant, in minor amount. Such fragrance compositions are quite usually proprietary blends of many different specific fragrance compounds. However, one of ordinary skill in the art, by routine experimentation, may easily determine whether such a proprietary fragrance composition is compatible in the

compositions of the present invention.

The inventive compositions may include one or more preservatives. Exemplary useful preservatives include compositions which comprise parabens, including methyl parabens and ethyl parabens, glyoxals, glutaraldehyde, formaldehyde, 2-bromo-2- nitropropoane-l,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3- one, and mixtures thereof. An exemplary preferred preservative composition based on isothiazoline compounds is ACTICIDE MBS (ex. Thor Group (UK), a division of Acti-Chem Specialties, Inc, Trumbull, CT) which includes both benzoisothiazoline and

methylisothiazoline. A further exemplary preferred preservative composition based on glyoxals includes ACTICIDE FN (ex. Thor Group (UK), described by its supplier as containing tetrahydroxymethylglyoxal diureaide. When present in a composition, in accordance with certain of the preferred embodiments, the preservative composition is advantageously present in amounts of up to about 1.5%wt, preferably are present in amounts of from about 0.0000 l%wt. to about 0.5%wt, and most preferably is present in an amount of from about 0.000 l%wt. to 0.1%wt. Particularly preferred preservative constituents and weight percentages thereof are described with reference to one or more of the Examples.

The compositions of the invention may include a water soluble or water dispersible thickener constituent in order to increase the viscosity of the compositions.

Thickeners useful in the present invention to achieve this viscosity are selected from the group consisting of polysaccharide polymers selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, or derivatives thereof, polycarboxylate polymers, polyacrylamides, clays, and mixtures thereof.

Examples of the cellulose derivatives include methyl cellulose ethyl cellulose, hydroxymethyl cellulose hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propyl methyl cellulose, ethylhydroxymethyl cellulose and ethyl hydroxy ethyl cellulose.

Examplary polycarboxylate polymers thickeners have a molecular weight from about 500,000 to about 4,000,000, preferably from about 1,000,000 to about 4,000,000, with, preferably, from about 0.5% to about 4% crosslinking. Preferred polycarboxylate polymers include polyacrylate polymers including those sold under trade names Carbopol®, Acrysol® ICS-1 and Sokalan®. The preferred polymers are polyacrylates. Other monomers besides acrylic acid can be used to form these polymers including such monomers as ethylene and propylene which act as diluents, and maleic anhydride which acts as a source of additional carboxylic groups.

Clay thickeners comprise, for example, colloid-forming clays, for example, such as smectite and/or attapulgite types. The clay materials can be described as expandable layered clays, i.e., aluminosilicates and magnesium silicates. The term "expandable" as used to describe the instant clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The expandable clays used herein are those materials classified geologically as smectites (or montmorillonite) and attapulgites (or polygorskites). Commercially available clays include, for example, montmorillonite, bentonite,

volchonskoite, nontronite, beidellite, hectorite, saponite, sauconite and vermiculite. The clays herein are available under various trade names such as Gelwhite GP, Gelwhite H, Mineral Colloid BP, and Laponite from Southern Clay Products, Inc., Texas; and Van Gel O from . T. Vanderbilt.

It is to be understood however that in many particularly preferred embodiments such a thickener constituent is necessarily excluded from the inventive compositions as sufficient viscosity is imparted by the judicious selection of the remaining constituents, particularly by the judicious selection of the surfactant constituents included in the compositions taught herein.

The inventive compositions may include one or more chelating agents as an optional constituent. Exemplary useful chelating agents include those known to the art, including by way of non-limiting example; aminopolycarboxylic acids and salts thereof wherein the amino nitrogen has attached thereto two or more substituent groups. Preferred chelating agents include acids and salts, especially the sodium and potassium salts of

ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N- hydroxyethylethylenediaminetriacetic acid, and of which the sodium salts of

ethylenediaminetetraacetic acid may be particularly advantageously used, e.g. tetrasodium ethylenediaminetetraacetic acid. Such chelating agents may be omitted, or they may be included in generally minor amounts such as from 0.001 - 0.5 %wt. based on the weight of the chelating agents and/or salt forms thereof.

To maintain or establish a desired pH of an inventive composition, the use of one or more pH buffers is contemplated. The compositions according to the invention optionally but desirably include an amount of a pH adjusting agent or pH buffer composition. Such compositions include many which are known to the art and which are conventionally used. By way of non-limiting example pH adjusting agents include phosphorus containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartrates and certain acetates. Further exemplary pH adjusting agents include mineral acids, basic compositions, and organic acids, which are typically required in only minor amounts. By way of further non-limiting example pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. It may also be suitable to use as buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, and their alkali metal salts. Desirably the inventive include an effective amount of an organic acid and/or an inorganic salt form thereof which may be used to adjust and maintain the pH of the treatment compositions of the invention to the desired pH range. Particularly useful are organic acids, e.g., citric acid and metal salts thereof such as sodium citrate which are widely available and which are effective in providing these pH adjustment and buffering effects. Further organic acids are also contemplated as being useful, including one or more compounds according to the formula:

R-COOH

wherein R is hydrogen, lower alkyl; substituted lower alkyl; hydroxy lower alkyl; carboxy lower alkyl; carboxy, hydroxy lower alkyl; carboxy, halo lower alkyl; carboxy, dihydroxy lower alkyl; dicarboxy, hydroxy lower alkyl; carboxy lower alkenyl; dicarboxy lower alkenyl; phenyl; substituted phenyl, wherein substituted lower alkyl is substituted by one or more groups consisting of halogen, hydroxyl, amino, thiol, nitro, and cyano. Examples of such organic acids include citric, malic, succinic, lactic, glycolic, fumaric, tartaric, and formic, and the like.

The compositions of the invention may also include one or more alkanolamines which may also be used to concurrently adjust the pH of the treatment composition. By way of nonlimiting examples such include monoalkanolamines, dialkanolamines,

trialkanolamines, and alkylalkanolamines such as alkyl-dialkanolamines, and dialkyl- monoalkanolamines. The alkanol and alkyl groups are generally short to medium chain length, that is, from 1 to 7 carbons in length. For di- and trialkanolamines and dialkyl- monoalkanolamines, these groups can be combined on the same amine to produce for example, methylethylhydroxypropylhydroxylamine. One of skill can readily ascertain other members of this group. Such alkanolamines may also provide an improved cleaning benefit particularly of greasy soils.

The inventive compositions may also comprise one or more hydrotropes, such as one or more anionic hydrotrope compounds. Exemplary hydtropes include, e.g., , benzene sulfonates, naphthalene sulfonates, Ci-Cn alkyl benzene sulfonates, naphthalene sulfonates, C5-C11 alkyl sulfonates, C6-Cn alkyl sulfates, alkyl diphenyloxide disulfonates, and phosphate ester hydrotropes. The hydrotropic compounds are often provided in a salt form with a suitable counterion, such as one or more alkali, or alkali earth metals, such as sodium or potassium, especially sodium. However, other water soluble cations such as ammonium, mono-, di- and tri- lower alkyl, i.e., C alkanol ammonium groups can be used in the place of the alkali metal cations. Exemplary alkyl benzene sulfonates include, for example, isopropylbenzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, as well as mixtures thereof. Exemplary C5-C11 alkyl sulfonates include hexyl sulfonates, octyl sulfonates, and hexyl/octyl sulfonates, and mixtures thereof. Particularly useful hydrotrope compounds include benzene sulfonates, o-toluene sulfonates, m-toluene sulfonates, and p- toluene sulfonates; 2,3-xylene sulfonates, 2,4-xylene sulfonates, and 4,6-xylene sulfonates; cumene sulfonates, wherein such exemplary hydrotropes are generally in a salt form thereof, including sodium and potassium salt forms.

As noted previously, when present, the cumulative total of the one or more foregoing optional constituents, when present in the inventive compositions, do not exceed about 10%wt, preferably do not exceed 8%wt, and most preferably do not exceed 5%wt. of the composition of which they form a part.

The compositions are largely aqueous in nature, and comprises as the balance of the composition water in to order to provide to 100% by weight of the compositions of the invention. The water may be tap water, but is preferably distilled and is most preferably deionized water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially mineral salts which are present in hard water which may thus undesirably interfere with the operation of the constituents present in the aqueous compositions according to the invention.

Preferred compositions of the invention are stable liquid, paste or gelled

compositions which do not undesirably degrade when subjected to an elevated temperature over an extended period of time. More specifically, the inventive compositions do not suffer precipitation or phase separation when a sample composition is subjected to an accelerated aging testing at 60°C, for a four-week test period. As is known to the art, such a test is a harsh test, and a useful indicator of the long term shelf stability of the tested sample composition. The inventive light duty dishwashing detergent compositions may be used for the manual washing of dishes and tableware but it is to be understood that the inventive compositions may also finds use in other areas as well including but not limited to: hard surface cleaning compositions, laundry pre spotter composition, detergent compositions used in the cleaning of floors, cabinetry, and other hard surfaces which may be present.

Additionally the inventive light duty dishwashing detergent compositions taught herein may be used as hand wash detergent soaps and/or for use as cleaning compositions for fibrous substrates such as carpets, rugs, mats, and the like. Thus while the primary benefit of the light duty dishwashing compositions according to the present invention find use in the cleaning of dishes and tableware, is to be understood that this is a preferred use and that use in other areas known for both light duty dishwashing detergent compositions as well as in other areas may also benefit from the use of the present inventive composition.

The following examples below illustrate exemplary formulations as well as preferred embodiments of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful formulations falling within the scope of the present invention and the claims may be readily produced by one skilled in the art without deviating from the scope and spirit of the invention.

Examples:

To demonstrate the compositions according to the invention, various formulations were prepared having the constituents which are indicated on Table 1 below wherein the amounts given are the weight percent of the identified compound, which was supplied from a respective raw material which was used "as supplied" from the respective supplier. The weight percentages of the compounds indicated on Table 1 are considered to be based on "100%wt. actives"; the sources of the compounds were supplied by the identified raw materials denoted on Table 2.

Preparation of the formulations were performed in a routine manner, which was generally in accordance with the following protocol. To a large glass beaker placed on a magnetic stirrer apparatus was added less than the total amount, or the total amount of deionized water. The temperature of the water, as well as that of the remaining constituents was approximately room temperature (≥68°F, =20°C) The stirrer apparatus was activated, and to the water was added measured amounts of each of the constituents. While order of addition of the constituents is not believed to be important, generally the surfactants were added to the stirring water and allowed to become well dispersed prior to the addition of the remaining constituents. After the addition of the final constituent, the contents of the beaker were allowed to stir for a period of 5 to 15 minutes to ensure homogeneous mixing and the production of a uniform formulation.

n.t. = not tested

viscosity (cPs) was measured at room temperature (20 - 25°C) on a Brookfield Type IV viscometer

The identity of the individual raw materials indicated on Tables 1 above, and commercial sources for these materials are described on the following Table 2. Table 2

nonionic surfactant, C12-C14 Ammonyx LO (30%wt. actives)

amine oxide

nonionic surfactant(1 ), Ninol 40-CO (100%wt. actives) ex. Stepan Co.

coconut diethanolamide

nonionic surfactant, lauryl Ninol 55L (100%wt. actives) ex. Stepan Co.

diethanolamide

nonionic surfactant(2), Rokamid KAD (100%wt. actives) ex. PCC Rokita SA cocodiethanolamide (Brzed Dolny, Poland)

anionic surfactant, sodium Steol CS 460 (60%wt. actives) ex. Stepan Co.

laureth sulfate

anionic surfactant, sodium Sulforokanol L370/1 (70%wt. actives) ex. PCC Rokita salt of fatty C ₁₂ -C ₁₄ alcohol SA (Brzed Dolny, Poland)

ether (3 EO) sulfate

anionic surfactant, sodium Crodasinic LS 30 (30%wt. actives) ex. Croda Inc. lauroyl sarcosinate

amphoteric surfactant(1 ), Amphotensid B4 (30%wt. actives) ex. Zschimmer & cocoamidopropyl dimethyl Schwarz

betaine

amphoteric surfactant(2), Empigen BS/FA (30%wt. actives) ex. Huntsman Chem. cocoamidopropyl betaine Co.

hydrotrope, sodium cumene Eltesol SC 40 (40%wt. actives)

sulfonate

monoethanlamine monoethanlamine (100%wt. actives)

sodium sulfate pH adjusting, anhydrous sodium sulfate (100%wt.

actives)

citric acid pH adjusting, anhydrous citric acid (100%wt. actives) preservative Acticide MSB, preservative composition (used "as supplied"), or Kathon CK, preservative composition (used "as supplied")

fragrance proprietary composition

colorant proprietary composition

Dl water deionized water

The total mass of the surfactant compounds present in each of the Example compositions, as well as the respective mass (weight) ratios of the anionic surfactant compound(s): amphoteric surfactant compound(s) present, and the respective mass (weight) ratios of the nonionic surfactant compound(s): amphoteric surfactant compound(s) present are indicated on the following Table 3. Table 3

E1 E2 E3 E4 E5 E6 total mass of 21.2 26 25 22.9 22.8 22.9 surfactant compounds

wt%/wt% ratio 5.29:1 5:1 5:1 5.37:1 5.13: 1 5.36:1 anionic:amphoteric

wt%/wt% ratio 3.81 :1 2.67:1 2.33:1 1.27:1 1.47: 1 1.26:1 nonionic:amphoteric

The cleaning efficacy of certain example compositions as well as one comparative composition was evaluated by determination of the number of uniformly soiled dinner plates which could be cleaned by the dishwashing liquor until no visible foam was present in the bowl. The test protocol used was closely based on that published under "Recommendation for the Quality Assessment of the Cleaning Performance of Hand Dishwashing Detergents", SOFW- Journal, 128. Jarhgang 5-2002, which is a known to the art. The general steps of this test protocol, and the specific steps used in the evaluation are as follows.

First a test soil was made from the following constituents, which were provided in the indicated weight percentages:

The test soil was made by providing the bulk of the water at room temperature to a large laboratory beaker supplied with a magnetic stirring rod. Then under stirring measured amounts of the other constituents were added in the following general sequence: fats (which if solid at room temperature, were heated to their melting point in order to liquefy them); followed by the powdered materials, and stirring continued until the test soil was well mixed. Thereafter the stirring rod was removed, and the container was placed overnight into a freezer in order to cool the composition. The following day, and on any subsequent day that the balance of the cleaning test were to be performed, the container was removed and the contents allowed to thaw and allowed to come to room temperature prior to being further used.

Prior to testing of cleaning efficacy of any composition, a series of standardized soiled plates were prepared according to the following general protocol.

To each of a series of machine dishwashed and dried ceramic or glass dinner plates was pipetted 6.7 g of the thawed test soil described above which was applied to the middle of each plate and allowed to spread without interference. The dinner plates were then stacked and ready for use in a subsequent cleaning test.

Cleaning testing was performed immediately subsequently to an evaluation of the aqueous dispersability of sample compositions as noted above.

Each of a number of plates was removed from the stack of standardized soiled plates and each was sequentially immersed for several seconds by hand into the dishwashing liquor, and while in this dishwashing liquor, the bristled end of a conventional dishwashing hand brush was manually applied under constant pressure to the soiled face of each plate and the bristles were moved in a circular motion five times on this side of the plate, and then the bristles were moved in a circular motion two times on the reverse or back side of the plate. Thereafter the treated dish was removed and stacked and allowed to dry. The cleaning of plated continued until it was visually observed that all foam on the surface of the

dishwashing liquor had dissipated or dispersed, although a minor amount of foam could be visible at the edges of the surface of the dishwashing liquor. The number of plates thus cleaned was recorded.

The foregoing test was performed for compositions according to Examples El - E5; the results of these tests are reported on the following Table 4:

As evident from the results reported, each of the compositions according to El provided excellent cleaning performance. The degree of foaming produced by aqueous dilutions of the El and E2 compositions according to Table 1 were evaluated in accordance with the following general protocol.

In each test, a sufficient amount of a tested composition was added to room temperature water standardized to a water hardness of 16 degrees hardness (+/- 2 degrees hardness) prepared per Recommendation for the Quality Assessment of the Cleaning Performance of Hand Dishwashing Detergents", SOFW- Journal, 128. Jarhgang 5-2002, in order to form a 0.05%wt. dilution of a tested composition in 100 milliliters of room temperature hard water, which mixture was then provided to a 250 milliliter graduated cylinder. The cylinder was then stoppered with a laboratory rubber stopper and inverted 20 times in order to generate foam. Immediately afterwards, the graduated cylinder was placed upon a laboratory table top and allowed to rest for 1-5 seconds, and the height of the foam, measured as the difference in the height (expressed as milliliters of the graduated cylinder) between the bottom of the foam layer formed at the top surface of the liquid in the graduated cylinder and the uppermost margin of the foam was determined and recorded. Subsequently, a 1 gram aliquot of cold pressed virgin olive oil was then pipetted into the graduated cylinder and the cylinder was restoppered, and again inverted 20 times in order to generate foam and then again, placed upon a laboratory table top and in a like manner, the foam height was determined and recorded. This latter sequence of addition of 1 gram aliquot cold pressed olive oil followed by inversions and measurement was repeated until 10 additional grams of the olive oil was added to the graduated cylinder. This test determined the height of the foam following the addition of the hydrophobic olive oil to the initial mixture of the product in water.

The results of this test are reported as indicated on the following table:

7 grams 10 18

8 grams 10 18

9 grams 10 17

10 grams 10 17

As is evident from the foregoing, the inventive compositions provided excellent foaming performance.