EP0758370A1

EP0758370A1 - Manual dishwashing compositions

Info

Publication number: EP0758370A1
Application number: EP95917666A
Authority: EP
Inventors: Peter Robert Foley; Paul Jerome Crabtree
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-05-05
Filing date: 1995-04-25
Publication date: 1997-02-19
Also published as: CA2191136A1; WO1995030729A1; CA2191136C; JPH09512852A; GB9408940D0; EP0758370A4

Abstract

The present invention relates to a dishwashing detergent composition comprising a surfactant system and high levels of hydrotrope for improved rinsing.

Description

MANUAL DISHWASHING COMPOSITIONS

Technical field of the Invention

The present invention relates to dishwashing detergent compositions comprising high levels of hydrotropes.

Background of the Invention

The formulator of a manual dishwashing detergent composition is required to formulate compositions which meet a number of consumer relevant performance demands.

Firstly, such a composition should be effective at removing soils from dirty "dishes" when used in a manual process. The soils encountered in dishwashing are largely but not exclusively food based. Particularly difficult soils to remove include greasy soils, burnt on food soils, dried on food soils, highly coloured soils derived from e.g. highly coloured vegetables, as well as non-food soils such as lipstick on the rims of glasses or nicotine stains.

Once the soils have been removed from the dishes the dishwashing detergent should act such as to suspend these soils in the wash solution and thus prevent their redeposition onto the dishes, or onto the su' ace of the sink.

In addition, the manual dishwashing composition should be high sudsing and the sudsing should persist throughout the washing process. This is particularly important as sudsing is used as an indicator by the consumer that the wash solution still contains active detergent ingredients. The consumer usually renews the wash solution when the sudsing has subsided .

The manual dishwashing composition should also be mild to the skin, and particularly to the hands and should not cause skin dryness, chapping or roughness. Such skin complaints largely result from the removal of natural oils from the skin. Thus, the manual dishwashing composition should desirably be effective at removing grease from plates but not natural oils from the skin. Reflecting the different nature of the performance demands for a manual dishwashing composition, such compositions are formulated in a distinct way from, for example, machine dishwashing, laundry, and hard-surface cleaner compositions.

In addition, due to environmental concerns the detergent manufacturers are striving towards producing more concentrated formulations and in order to minimise the impact the formulations and their packaging have on the environment.

However, it has been noticed that this concentration results in high active dishwashing formulations that require an increase in the amount of rinsing in order to remove detergent compositions from the dish article once manual agitation is complete. For example, in direct application conditions the dish article is dampened and the detergent composition is applied to the dish article in a highly concentrated form or even in its undiluted form. After manual agitation by the consumer, the article is placed under running water to be rinsed. The article is thus held under the running water until the consumer is satisfied that the remaining detergent composition on the dish article has been removed. Completion of rinsing is often evaluated by the complete removal of suds from the dish article and by the lack of a greasy or slippery feel of the dish article to the touch. Under certain consumer washing conditions such as in ambient water conditions and direct application conditions this problem of complete rinsing is particularly noticeable.

It is therefore an aim of the present invention to provide a concentrated dishwashing detergent composition which exhibits improved rinsing performance.

It has now been found that this objective can be achieved by the incorporation of high levels of hydrotropes in the dishwashing formulations.

Hydrotropes are known in the art and have been described for various applications. Hydrotropes are typically incorporated into liquid detergent compositions in order to increase the aqueous solubility of various slightly soluble organic chemicals, particularly surfactants. In order to aid dissolution the art teaches that low levels of hydrotrope, i.e. less than 10% are required to deliver the benefit.

For example EP 396340 discloses hard surface cleaning compositions comprising anionic and nonionic surfactants and hydrotropes. Dishwashing compositions are also exemplified. EP 467618 discloses liquid hard surface cleaners comprising pine oil, chelating agents and hydrotropes. Dishwashing compositions are not mentioned.

Higher levels of hydrotrope have been disclosed in the art. For example EP 200264 discloses concentrated heavy duty liquid detergent compositions comprising anionic and nonionic surfactants and 2-50% water soluble dicarboxylic acid monoester (a hydrotrope). No other hydrotropes or dishwashing compositions are disclosed.

GB 1 380 107 discloses liquid detergent compositions comprising organic detergents and 1-40% hydrotrope. Dishwashing compositions are not disclosed.

Unpublished US patent application number 07/938978 discloses liquid dishwashing compositions comprising polyhydroxy fatty acid amide and 0.001-15%) alkylpolyethoxy carboxylate (disclosed as a hydrotrope). US patent number 07/938979 discloses liquid dishwashing compositions comprising 5-95% alkylamphocarboxylic acid and calcium or magnesium ions.

However, the art does not recognise the rinsing performance benefits that are provided to high active dishwashing detergent compositions by the incorporation of high levels of hydrotrope.

Summary of the invention

The present invention is a dishwashing detergent composition comprising a surfactant system, said system comprising a polyhydroxyfatty acid amide and/or a alkylpolysaccharide or mixtures thereof and,

greater than 11% hydrotrope selected from lower alkyl aryl sulphonate salts, Cβ-C^ alkanols, C1-C6 carboxylic sulphate or sulphonate salts, urea, C1-C4 hydrocarboxylates, C1-C4 carboxylates and C2-C4 diacids and mixtures thereof.

All weights, ratios and percentages are given as a % weight of the total composition unless otherwise stated.

Detailed description of the invention

Hydrotropes According to the present invention an essential feature of the dishwashing detergent composition is a hydrotrope. Hydrotropes suitable for use herein are selected from the group lower alkyl aryl sulphonate salts, Cg-Ci 2 alkanols, Ci -Cβ carboxylic sulphate or sulphonate salts, urea, C1-C4 hydrocarboxylates, C1 -C4 carboxylates and C2-C4 diacids and mixtures thereof.

Suitable lower alkyl aryl sulphonates are preferably C7-C9 alkyl aryl sulphonates and include sodium, potassium, calcium and ammonium xylene sulphonates, sodium, potassium, calcium and ammonium toluene sulphonates, sodium, potassium, calcium and ammonium cumene sulphonate, and sodium, potassium, calcium and ammonium napthalene sulphonates and mixtures thereof.

Suitable Cj-Cg carboxylic sulphate or sulphonate salts are any water soluble salts or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent groups), which are substituted with sulphate or sulphonate and have at least one carboxylic group. The substituted organic compound may be cyclic, acylic or aromatic, i.e. benzene derivatives. Preferred alkyl compounds have from 1 to 4 carbon atoms substiuted with sulphate or sulphonate and have from 1 to 2 carboxylic groups. Examples of suitable hydrotropes include sulphosuccinate salts, sulphophthalic salts, sulphoacetic salts, m- sulphobenzoic acid salts and diesters sulphosuccinates, preferably the sodium or potassium salts as disclosed in US 3 915 903.

Suitable C1-C4 hydrocarboxylates, C1-C4 carboxylates for use herein include acetates and propionates and citrates. Suitable C2-C4 diacids for use herein include succinic, glutaric and adipic acids.

Other compounds which deliver hydrotropic effects suitable for use herein as a hydrotrope include Cg-Ci2 alkanols and urea.

Preferred hydrotropes for use herein are sodium, potassium, calcium and ammonium cumene sulphonate, sodium, potassium, calcium and ammonium xylene sulphonate, sodium, potassium, calcium and ammonium toluene sulphonate and mixtures thereof. Most preferred are sodium cumene sulphonate and calcium xylene sulphonate and mixtures thereof. According to the present invention the dishwashing compositions comprise more than 11% of said hydrotrope, preferably from 11.5% to 40%, more preferably from 12% to 25%o, most preferably from 12% to 20% of said hydrotrope and mixtures thereof.

Another essential feature of the present invention is a surfactant system. Said surfactant system comprises as an essential feature a alkylpolysaccharide and/or a polyhydroxy fatty acid amide or mixtures thereof. The compositions of the present invention comprise from 1% to 50%, preferably from 5% to 40%, more preferably from 10%) to 40%) of said surfactant system.

Alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.0 to about 10, preferably from about 1.0 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.)

The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. Optionally, and less desirably, there can be a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide.

Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galatoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides. The preferred alkylpolyglycosides have the formula: R2θ(C_nH_2nO)t(glycosyl)_x

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7, x is from 1.0 to 10, preferably from 1.0 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1 -position and the preceding glycosyl units 2-,3-, 4- and/or 6-position, preferably predominantly the 2-position. In addition to the polysaccharides mentioned above the corresponding sulphated polysaccharides may also be used herein.

According to the present invention the dishwashing compositions comprise from 0%) to 50%), preferably from 1% to 30%, more preferably from 1.5% to 20% of said alkylpolysaccharide surfactant.

Polyhydroxy fatty acid amide surfactant

Poly hydroxy fatty acid amides suitable for use herein are according to the formula:

R₂-C-N-Z O R! wherein R is H, a Cι_C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, preferably a C1-C4 alkyl, more preferably a C\ or C2 alkyl, most preferably a Ci, and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl or mixtures thereof; and Z is a polyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain or an alkoxylated derivative thereof. Z is preferably derived from a reducing sugar in reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be utilised as well as individual sugars listed above. It should be understood that these com syrups may yield a mixture of sugar components for Z. Z is preferably selected from the group consisting of -CH₂(CHOH)nCH₂OH, -CH(CH₂OH)-(CHOH)n-l-CH₂OH, or -CH₂-

(CHOH)2(CHOR)(CHOH)-CH₂OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 inclusive and R' is hydrogen or a cyclic or aliphatic mono saccharide. Most preferred are the glycityls wherein n is 4, particularly CH2(CHOH)4CH2OH.

According to the formula R\ can be for example, N-methyl , N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R5~CO-N< can be for example cocamide, stearimide, oleamide, lauramide, myristamide, capricamide, palmitamide, talloamide etc. Z can be 1-deooxyglycityl, 2-deoxyfructityl, 1- deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-doexymannityl, 1- deoxymaltotriotityl, etc.

Other polyhydroxy fatty acid amides suitable for use herein are gemini polyhydroxy fatty acid amides having the formula:

Z Z

I I

N-X-N

0=C C=0 I I R R'

wherein: X is a bridging group having from about 2 to about 200 atoms; Z and Z' are the same or different alcohol-containing moieties having two or more hydroxyl groups (e.g., glycerol, and units derived from reducing sugars such as glucose, maltose and the like), or either one (but not both) of Z or Z' is hydrogen; and R and R* are the same or different hydrocarbyl moieties having from about 1 to about 21 carbon atoms and can be saturated, branched or unsaturated (e.g., oleoyl) and mixtures thereof.

Preferred X groups are selected from substituted or unsubstituted, branched or linear alkyl, ether alkyl, amino alkyl, or amido alkyl moieties having from about 2 to about 15 carbon atoms. Preferred alkyl moieties are unsubstituted, linear alkyl moieties having the formula -(CH2)_n-, wherein n is an integer from 2 to about 15, preferably from 2 to about 10, and most preferably from 2 to about 6; and also unsubstituted, branched alkyl moieties having from 3 to about 15 carbon atoms, preferably from 3 to about 10 carbon atoms, and most preferably from 3 to about 6 carbon atoms. Most preferred are ethylene and propylene (branched or linear) alkyl moieties. Also preferred are unsubstituted, branched or linear ether alkyl moieties having the formula -R2-(O-R2)_m-, wherein each R^ is independently selected from C2-Cg branched or linear alkyl and or aryl moieties (preferably ethyl, propyl or combinations thereof) and m is an integer from 1 to about 5. X may also be unsubstituted, branched or linear amino and or amido alkyl moieties having the formula -R2-(N(R3)-R2)_m-₎ wherein each R^ is independently selected from C2-C branched or linear alkyl and or aryl moieties (preferably ethyl, propyl or combinations thereof), m is an integer from 1 to about 5, and R- is selected from hydrogen, C1-C5 alkyl, and -C(O)R⁴-, wherein R⁴ is C -C21 alkyl, including -C(O)R. The X moiety may be derived from commercially available amine compounds such as, for example, Jeffamines^ (supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 and J-D400.

Preferred X moieties therefore include: -(CH₂)2-, -(CKtøtø-, -(CH2 4-, -(CH2)s-, - (CH₂)₆-, -CH₂CH(CH3)(CH₂)3-, -(CH₂)2-O-(CH₂)2-, -(CH₂)3-O-(CH₂)3-, -(CH₂)₂-O- (CH₂)₃-, -(CH₂)2-O-(CH2)2-O-(CH₂)2-, -(CH₂)3-O-(CH2)2-O-(CH₂)3-₎ -(CH₂)₂-O- (CH₂)3-0-(CH₂)2-, -(CH₂)2-NH-(CH₂)2-, -(CH₂)3-NH-(CH2)3-, -(CH₂)2-NH-(CH₂)3- , -(CH₂)2-N(C(O)R)-(CH₂)2-, -(CH₂)₃-N(C(O)R)-(CH₂)3-, -(CH₂)₂-N(C(O)R)- (CH₂)₃-, -(CH₂)2-NH(C₆H₄)NH-(CH2)2-, -(CH₂)3-NH(C₆H₄)NH-(CH₂)3-, -(CH₂)₂- NHCH2(C₆H₄)CH₂NH-(CH₂)2-, -(CH2)3-NHCH2(C₆H4)CH2NH-(CH₂)3-. etc.

Preferred Z and Z" groups are independently selected from polyhydroxyhydrocarbyl moieties having a linear hydrocarbyl chain with at least 2 hydroxyls (in the case of glycerol) or at least 3 hydroxyls ( in the case of other sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z and Z' preferably will be derived from a reducing sugar, more preferably Z and or Z' is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose com syrup, high fructose com syrup, and high maltose com syrup can be utilised as well as the individual sugars listed above. These com syrups may yield a mix of sugar components for Z and Z'. It should be understood that it is by no means intended to exclude other suitable raw materials. Z and/or Z' preferably will be selected from the group consisting of -CH2- (CHOH)-_p-CH₂OH, -CH(CH₂OH)-(CHOH)p.ι-CH₂OH, -CH₂-

(CHOH)₂(CHOR¹)(CHOH)-CH₂OH, where p is an integer from 1 to 5, inclusive, and R¹ is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. . Most preferred are glycityls wherein p is 4, particularly -CH2-(CHOH)4-CH2OH.

Preferred R and R' groups are independently selected from C3-C21 hydrocarbyl moieties, preferably straight or branched chain C3-C13 alkyl or alkenyl, more preferably straight chain C5-C11 alkyl or alkenyl, most preferably straight chain C5-C9 alkyl or alkenyl, or mixtures thereof. R-CO-N< and/or R'-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Examples of such compounds therefore include, but are not limited to:

CH3(CH₂)6C(O)N[CH2(CHOH)₄CH2θH]-(CH₂)2-

[CH2(CHOH)4CH2OH]NC(O)(CH₂)6CH₃; CH₃(CH2)8C(O)N[CH2(CHOH)₄CH₂OH]- (CH2)2-[CH2(CHOH)4CH2OH]NC(O)(CH2)8CH₃;

CH₃(CH2)ioC(O)N[CH2(CHOH)₄CH2OH]-(CH₂)2- [CH2(CHOH)4CH2OH]NC(O)(CH₂)₁₀CH3;

CH3(CH2)8C(O)N[CH2(CHOH)₄CH₂OH]-(CH2)2-0-(CH2)2-O-(CH2)2- [CH2(CHOH)₄CH₂OH]NC(O)(CH2)8CH₃; CH₃(CH2)8C(O)N[CH₂(CHOH)₄CH₂OH]- CH2CH(CH3)(CH2)3-[CH2(CHOH)₄CH₂OH]NC(O)(CH2)8CH3;

CH3(CH2)8C(O)N[CH2(CHOH)₄CH₂OH]-(CH2)3-O-(CH2)2-0-(CH2)3- [CH2(CHOH)₄CH₂OH]NC(O)(CH2)8CH₃;

CH3(CH₂)3CH(CH2CH3)C(O)N[CH2(CHOH)4CH₂OH]-(CH2)2- [CH₂(CHOH)4CH2OH]NC(O)CH(CH2CH3)(CH2)3CH₃; CH3(CH2)₆C(O)N[CH2(CHOH)₄CH₂OH]-(CH2)3-O-(CH2)2-O-(CH₂)3- [CH2(CHOH)4CH₂OH]NC(O)(CH₂)6CH3 ; CH₃ (CH₂)₄C(O)N[CH₂(CHOH)₄CH₂OH]- (CH2)3-O-(CH2)2-0-(CH2)3-[CH2(CHOH)₄CH₂OH]NC(O)(CH2)8CH3; C₆H5C(O)N[CH2(CHOH)4CH₂OH]-(CH2)3-O-(CH2)2-O-(CH2)3- [CH₂(CHOH)4CH₂OH3NC(O)C₆H5; CH₃(CH₂)₄C(O)N[CH₂(CHOH)₄CH₂OH]-

(CH₂)₂-[CH₂(CHOH)₄CH₂OH]NC(O)(CH₂)8CH₃.

These compounds can be readily synthesised from the following disugar diamines: HN[CH₂(CHOH)₄CH₂OH]-(CH₂)₂-[CH₂(CHOH)₄CH₂OH]NH; HN[CH₂(CHOH)₄CH₂OH]-CH₂CH(CH3)(CH₂)3-[CH₂(CHOH)4CH₂OH]NH; HN[CH2(CHOH)4CH2θH]-(CH₂)2-O-(CH2)2-O-(CH2)2-[CH2(CHOH)4CH2θH]NH; HN[CH2(CHOH)4CH2OH]-(CH2)3-O-(CH₂)2-O-(CH₂)3-[CH₂(CHOH)4CH₂OH]NH; and HN[CH₂(CHOH)4CH2θH]-(CH2)3-[CH2(CHOH)₄CH2θH]NH.

The compositions according to the present invention comprise from 0% to 50% , preferably from 1% to 20%, most preferably from 3% to 15%, of said polyhydroxy fatty acid amide.

Surfactant system According to the present invention the surfactant system may optionally comprise other surfactants selected from nonionic, anionic, cationic, zwitterionic, and amphoteric surfactants, and any mixtures thereof.

The anionic surfactant may be essentially any anionic surfactant, including anionic sulphate, sulphonate or carboxylate surfactant.

Anionic sulphate surfactant

The anionic sulphate surfactant mf-.y be any organic sulphate surfactant. It is preferably selected from the group consisting of C10-C16 alkyl sulphate which has been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule, C9- C17 acyl-N-(Cι-C₄ alkyl) glucamine su'phated, -N-(C2-C₄ hydroxyalkyl) glucamine sulphate, and mixtures thereof. More preferably, the anionic sulphate surfactant is a ClO"Cl6 alkyl sulphate which has been ethoxylated with from about 0.5 to about 20, preferably from about 0.5 to about 12, moles of ethylene oxide per molecule.

Alkyl ethoxy sulphate surfactants comprises a primary alkyl ethoxy sulphate derived from the condensation product of a C10-C16 alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 12, ethylene oxide groups. The C10-C16 alcohol itself is commercially available. C12-C 4 alkyl sulphate which has been ethoxylated with from about 3 to about 10 moles of ethylene oxide per molecule is preferred.

Conventional base-catalysed ethoxylation processes to produce an average degree of ethoxylation of 12 result in a distribution of individual ethoxylates ranging from 1 to 15 ethoxy groups per mole of alcohol, so that the desired average can be obtained in a variety of ways. Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent processing steps such as distillation.

Anionic sulphate surfactants include the C9-C 7 acyl-N-(Cι-C4 alkyl) and -N-(C - C2 hydroxyalkyl) glucamine sulphates, preferably those in which the C9-C17 acyl group is derived from coconut or palm kernel oil. These materials can be prepared by the method disclosed in U.S. Patent 2,717,894, Schwartz, issued September 13, 1955. The counterion for the anionic sulphate surfactant component is preferably selected from calcium, sodium, potassium, magnesium, ammonium, or alkanol-ammonium, and mixtures thereof, with calcium and magnesium being preferred for cleaning and sudsing, respectively.

Anionic sulphonate surfactant

Anionic sulphonate surfactants suitable for use herein include, for example, the salts (e.g. alkali metal salts) of C9-C20 linear alkylbenzene sulphonates, C -C22 primary or secondary alkane sulphonates, C8-C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, paraffin sulphonates, and any mixtures thereof.

Anionic alkyl ethoxy carboxylate surfactant

Alkyl ethoxy carboxylates suitable for use herein include those with the formula RO(CH2CH2θ)x CH2C00-M+ wherein R is a C_i2 to C 6 alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20%, preferably less than 15%, most preferably less than 10%), and the amount of material where x is greater than 7, is less than 25%, preferably less than 15%, most preferably less than 10%, the average x is from 2 to 4 when the average R is C 3 or less, and the average x is from 3 to 6 when the average R is greater than C 3, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium mono., di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl ethoxy carboxylates are those where R is a C 12 to C 14 alkyl group.

Anionic alkyl polvethoxy polvcarboxylate surfactant

Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula:

R - O -(CH - CH - O)x - R3

I I

Rl R₂

wherein R is a Cg to C\% alkyl group, x is from 1 to 25, R\ and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, wherein at least one Ri or R₂ is a succinic acid radical or hydroxysuccinic acid radical, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Anionic secondary soap surfactant

Secondary soap surfactants (aka "alkyl carboxyl surfactants") useful herein are those which contain a carboxyl unit connected to a secondary carbon. It is to be understood herein that the secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. The secondary soap surfactants should contain no ether linkages, no ester linkages and no hydroxyl groups. There should be no nitrogen atoms in the head-group (amphiphilic portion). The secondary soap surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.

The following general structures further illustrate some of the secondary soap surfactants (or their precursor acids) useful herein.

A. A highly preferred class of secondary soaps useful herein comprises the secondary carboxyl materials of the formula R- CH(R )COOM, wherein R-* is CH3(CH₂)x and R⁴ is CH3(CH2)y, wherein y can be 0 or an integer from 1 to 4, x is an integer from 4 to 10 and the sum of (x + y) is 6-14, preferably 7-13, most preferably 12.

B. Another class of secondary soaps useful herein comprises those carboxyl compounds wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e., secondary soaps of the formula R⁵-R⁶-COOM, wherein R⁵ is C⁷-C¹⁰, preferably C⁸-C⁹, alkyl or alkenyl and R is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R^ can be in the ortho, meta or para position relative to the carboxyl on the ring.)

C. Still another class of secondary soaps comprises secondary carboxyl compounds of the formula CH₃(CHR)_k-(CH₂)_m-(CHR)_n-CH(COOM)(CHR)₀-(CH2)p-(CHR)_q-CH3, wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18. In each of the above formulas A- B and C, the species M can be any suitable, especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri- alkanolammonium, and C1-C5 alkyl substituted ammonium. Sodium is convenient, as is diethanolammonium.

Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l-octanoic acid, 2- pentyl-1-heptanoic acid and isopentadecanoic acid.

Other anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium- potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, fatty oleyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates, N-acyl sarcosinates, branched primary alkyl sulphates, alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)_kCH₂COO-M⁺ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with isethionic acid and neutralised with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.

According to the present invention the dishwashing compositions may comprise from 3% to 50%), preferably from 3% to 40%, more preferably from 3% to 30% of said anionic surfactant.

Nonionic surfactant

According to the present invention the surfactant system of said dishwashing detergent composition may comprise nonionic surfactants. Nonionic condensates of alkyl phenols

Nonionic condensates suitable for use herein include polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.

Nonionic ethoxylated alcohol surfactant

Alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred are the condensation products of alcohols having an alkyl group containing from 8 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 1 -C15 linear alcohol with 9 moles ethylene oxide), Tergito.TM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol^τM ₄5-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodo.TM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.54 moles of ethylene oxide), NeodofT 45.7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodo.TM 45.4 (the condensation product of C14-C 5 linear alcohol with 4 moles of ethylene oxide), Neodo.TM 23.3 (the condensation product of C 12-13 linear alcohol with 3 moles of ethylene oxide) marketed by Shell Chemical Company, and Kyro™ EOBN (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company and Dobanol 91 marketed by the Shell Chemical Company and Lial 111 marketed by Enichem.

Nonionic EO PO condensates with propylene glvcol

The condensation products of ethylene oxide (EO) with a hydrophobic base formed by the condensation of propylene oxide (PO) with propylene glycol are suitable for use herein. Examples of compounds of this type include certain of the commercially- available Pluronic surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diamine adducts

The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic^τM compounds, marketed by BASF.

According to the present invention the dishwashing compositions may comprise from 0%) to 30%), preferably from 0.1% to 25%, more preferably from 0.5% to 20% of said nonionic surfactants.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula:

O

II

RC-NHCH₂CH₂Ri

wherein R is a Cs-Ci alkyl group, and Rj is of the general formula

(CH₂)_xC00- (CH₂)_xC00-

N or N(⁺)-CH₂CH₂OH

Rl Rl

wherein R¹ is a (CH2)_xCOOM or CH2CH2OH, and x is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri- ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred R alkyl chain length is a C Q to C 4 alkyl group. A preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid. A suitable example of an alkyl aphodicarboxylic acid for use herein in the amphoteric surfactant Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Amine oxide surfactant

The compositions of the present invention preferably further comprise from 1% to 20%), preferably from 2% to 20% by weight of an amine oxide.

Amine oxides useful in the present invention include those compounds having the formula :

O

I

R3(OR⁴)_XN(R5)₂

wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms; R⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3, preferably 0; and each R5 is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups. The R^ groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include Cio-Cig alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2- hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C o-Cig alkyl dimethylamine oxide, and C10-I8 acylamido alkyl dimethylamine oxide.

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions herein.

Betaine surfactants

According to the present invention the compositions may comprise betaines. The betaines useful as zwitterionic surfactants in the present invention are those compounds having the formula wherein R is a Cg-Cis hydrocarbyl group, preferably a C10-C16 alkyl group or C10-I6 acylamido alkyl group, each is typically C1-C3 alkyl, preferably methyl, and R² is a C1-C5 hydrocarbyl group, preferably a Ci- C3 alkylene group, more preferably a C1-C2 alkylene group. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[Ci4_i6 acylmethylamidodiethylammonio]- 1 -carboxybutane; C 15.18 acylamidodimethylbetaine; C12-I6 acylamidopentanediethyl-betaine; [C12-I6 acylmethylamidodimethylbetaine. Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the C10-I8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.

The complex betaines for use herein have the formula

R - (A)_n - [N - (CHRι)_x]_y - N - Q (I)

I I

B B wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, A is the group (C(O)), n is 0 or 1, R is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer of 0 to 4, Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium and B is hydrogen or a group Q as defined.

Sultaines

The sultaines useful in the present invention are those compounds having the formula (R(R¹)2N⁺R²S03" wherein R is a Cg-C^ hydrocarbyl group, preferably a Clθ" l6 ^a' group, more preferably a C 2-C13 alkyl group, each Rl is typically C - C3 alkyl, preferably methyl, and R² is a C -Cg hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines include C12-C 4 dimethylammonio-2-hydroxypropyl sulfonate, C12-14 amido propyl ammonio- 2-hydroxypropyl sultaine, C12-.14 dihydroxyethylammonio propane sulfonate, and Ci6_ 18 dimethylammonio hexane sulfonate, with C12-14 amido propyl ammonio-2- hydroxypropyl sultaine being preferred.

The zwitterionics described herein above may also be presen tin small quantities to deliver suds enhancing benefits to the compositions.

Enzymes

Compositions according to the present invention may additionally comprise enzymes. Suitable enzymes for use herein include lipolytic, proteolytic and amyloyltic enzymes. A preferred lipase is derived from Pseudomonas pseudoalcaligenes described for example in EP-B-0218272. Preferred commercially available proteolytic enzymes include Alcalase and Savinase (Novo Industries A/S) and Maxatase (International Bio- Synthetics, Inc.). Preferred amylases include for example alpha-amylases obtained from a special strain of B licheniforms, described for example in GB 1 269 839. Preferred commercially available amylases include Termamyl (Novo Industries A/S). The compositions according to the present invention may comprise from 0.001% to 1%, more preferably from 0.01%) to 0.1% of active enzyme. In addition the composition may comprise an enzyme stabilizing system.

Lime Soap Dispersants

The compositions of the present invention are particularly useful when formulated to contain a lime soap dispersant compound which acts to disperse any insoluble lime soap salts formed. Lime soaps prevent the deposition of these salts as spots or films on the articles in the wash, or as an unseemly ring around the rim of the sink. Certain lime soap dispersant compounds may also provide improved product stability particularly where the product is formulated as a liquid product containing calcium ions.

A lime soap dispersant compound herein is defined as a compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap dispersant compound is typically present at a level of from 0.1 % to 40% by weight, more preferably 1% to 20%> by weight, most preferably from 2% to 10% by weight of the compositions. A lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions. A numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950). The LSDP is the % we^'ght ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in 30ml of water of 333ppm CaCO3 (Ca:Mg=3:2) equivalent hardness.

Thus in accord with the test method described above a material with a lower LSDP is a more effective lime soap dispersant than one with a higher LSDP.

Calcium

According to the present invention the dishwashing compositions may comprise from 0.01%) to 3%>, more preferably from 0.15% to 1% of calcium ions may be included in the detergent compositions herein. It has been found for compositions containing polyhydroxy fatty acid amide that the presence of calcium greatly improves the cleaning of greasy soils. This is especially true when the compositions are used in softened water, which contains few divalent ions.

The calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt. If the anionic surfactants are in the acid form, the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.

The calcium ions may be present in the compositions as salts. The amount of calcium ions present in compositions of the invention may be dependent upon the amount of total anionic surfactant present herein. The molar ratio of calcium ions to total anionic surfactant is preferably from 1 :0.1 to 1:25, more preferably from 1:2 to 1:10, for compositions of the invention.

Calcium stabilising agent

Malic, maleic or acetic acid or certain lime soap dispersant compounds may be added to a composition formulated to contain calcium to provide good product stability, and in particular to prevent the precipitation of insoluble calcium salts. Malic, maleic or acetic acid may, where calcium is present, preferably be added at levels of from 0.05% to 10% of the composition and a molar ratio with calcium of from 10:1 to 1:10.

Magnesium

From 0.01%) to 3%, most preferably from 0.15%) to 2%, by weight, of magnesium ions are preferably added to the liquid detergent compositions of the invention for improved product stability, as well as improved sudsing.

If the anionic surfactants are in the acid form, then the magnesium can be added by neutralization of the acid with a magnesium oxide or magnesium hydroxide slurry in water. Calcium can be treated similarly. This technique minimises the addition of chloride ions, which reduces corrosive properties. The neutralised surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.

Organic solvent

The compositions of the invention will most preferably contain an organic solvent system present at levels of from 1%> to 30% by weight, preferably from \% to 20% by weight, more preferably form 2% to 15%> by weight of the composition. The organic solvent system may be a mono, or mixed solvent system; but is preferably in mixed solvent system. Preferably, at least the major component of the solvent system is of low volatility. Suitable organic solvents for use herein has the general formula:

CH₃

RO(CH₂CHO)_nH

wherein R is an alkyl, alkenyl, or alkyl aryl group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4. Preferably, R is an alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2. Especially preferred R groups are n-butyl or isobutyl. Preferred solvents of this type are l-n-butoxypropane-2-ol (n=l); and l(2-n-butoxy-l- methylethoxy)propane-2-ol (n=2), and mixtures thereof.

Other solvents useful herein include the water soluble CARBITOL or CELLOSOLNE solvents. These solvents are compounds of the 2-(2- alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl.

Other suitable solvents are benzyl alcohol, and diols such as 2-ethyl-l,3- hexanediol and 2,2,4-trimethl-l,3-pentanediol.The low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.

The alkane mono and diols, especially the Cι-C6 alkane mono and diols are suitable for use herein. C1-C4 monohydric alcohols (eg: ethanol, propanol, isopropanol, butanol and mixtures thereof) are preferred, with ethanol particularly preferred. The Cl- C4 dihydric alcohols, including propylene glycol, are also preferred.

Thickening agents The compositions according to the present invention may addditionally comprise thickening agents, such as polyquaterium cellulose cationic polymer, for example Quatrisoft available from the Americhol Corporation.

pH of the Composition

The compositions according to the present invention formulated for use in manual dishwashing applications are preferably formulated to have a pH at 20 C of from 3 to 12, preferably from 6 to 9, most preferably from 7 to 8.5.

In another aspect of the present invention the composition may be formulated for use as in pre-treatment applications whereby the composition is applied in essentially the concentrated from onto the dishes. Preferably the composition is allowed to remain on the dishes for a period of time. Compositions for use in such applications preferably have a pH of from 3 to 14, more preferably from 3 to 5 or greater than 8.

Detergent compositions

According to the present invention the compositions may be liquid or gel compositions.

Liquid compositions

In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. In one preferred embodiment of the present invention the compositions are high active formulations such that said compositions comprise 75% to 50% by weight, preferably from 70%> to 55% by weight, most preferably from 65% to 55%) by weight of a liquid carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred monohydric alcohol or a mixture of water and C1-C4 dihydric alcohol (e.g.: propylene glycol). In another preferred embodiment of the present invention the detergent composition may be in a concentrated form, such that the composition is diluted in water prior to usage.

Gels The detergent compositions of the present invention may also be in the form of a gel. Such compositions are typically formulated in polyakenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.

Highly preferred examples of these polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. It is believed that these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.

The polycarboxylate polymer thickener is utilised preferably with essentially no clay thickening agent. In fact, it has been found that if the polycarboxylate polymers of the present invention are utilised with clay in the composition of the present invention, a less desirable product, in terms of phase instability, results. In other words, the polycarboxylate polymer is preferably used instead of clay as a thickening/stabilising agent in the present compositions.

If the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2%> to about 2%> by weight.

The thickening agents are preferably used to provide a yield value of from about 50 to about 350 and most preferably from about 75 to about 250. The yield value is an indication of the shear stress at which the gel strength is exceeded and flow is initiated. It is measured herein with a Brookfield RNT model viscometer with a T-bar B spindle at 25°utilizing a Helipath.

Other desirable ingredients typically used in the compositions herein include dyes, perfumes and opacifiers.

Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex, or ethylene glycol distearate can be added, preferably as a last step. Lytron can be added directly as a dispersion with mixing. Ethylene glycol distearate can be added in a molten state with rapid mixing to form pearlescent crystals. Opacifiers useful herein, particularly for light duty liquids, are typically present at levels from about 0.2% to about 10%, preferably from about 0.5% to about 6% by weight.

Manual dishwashing process

According to the manual dishwashing process aspect of this invention, soiled dishes are contacted with an effective amount, typically from about 0.5 ml. to about 20 ml. (per 25 dishes being treated), preferably from about 1ml. to about 10 ml., of the composition of the present invention. The actual amount of liquid detergent composition used will be based on the judgement of user, and will depend upon factors such as the particular product formulation of the composition, the concentration of the composition, the number of soiled dishes to be cleaned, the degree of soiling of the dishes and the process used by the consumer.

The process by which the soiled dishes are contacted with the effective amount of the composition of the invention may be essentially any of the processes for manual dishwashing commonly known and encompasses the dilute solution in sink process, commonly used in Northern Europe and the US ; the solution in bowl process, commonly used in Latin America, and the direct application process, commonly used in Southern Europe, Japan, and developing countries.

Dilute solution in sink process

In the typical dilute solution in sink process from about 3 ml. to 15 ml., preferably from 5 ml. to 10 ml. of a liquid detergent composition is combined with from 1,000 ml. to 10,000 ml., more typically from 3,000 ml. to 5,000 ml. of water in a sink having a volumetric capacity in the range of from 5,000 ml. to 20,000 ml., more typically from 10,000 ml. to 15,000 ml. The detergent composition has a surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 45 % to about 50 % by weight. The soiled dishes are immersed in the sink containing the detergent composition and water, where they are cleaned by contacting the soiled surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.

Solution in bowl process

In a typical solution in bowl process from 1 ml. to 50 ml., preferably from 2 ml. to 10 ml. of a detergent composition is combined with from 50 ml. to 2,000 ml., more typically from 100 ml. to 1,000 ml. of water in a bowl having a volumetric capacity in the range of from 500 ml. to 5,000 ml., more typically from 500 ml. to 2,000 ml. The detergent composition has a surfactant concentration of from about 10 % to about 60 % by weight, preferably from about 15 % to about 50 % by weight. The soiled dishes are cleaned by contacting the soiled surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article may be immersed in the detergent composition and water mixture prior to being contacted with the dish surface and is typically contacted with the dish surface for a period of time ranging from about 1 to about 10 seconds, although the actual time will vary with each application and user. The contacting of the cloth, sponge or similar article to the dish surface is preferably accompanied by a concurrent scrubbing of the dish surface.

Direct Application Process

The direct application process will typically comprise as a first step immersing the soiled dishes into a water bath without any liquid dishwashing detergent or holding the dishes under running water. A device for absorbing liquid dishwashing detergent, such as a sponge, is then placed directly into a separate quantity of undiluted liquid or gel detergent composition for a period of time typically ranging from about 1 to about 5 seconds. Alternatively, the dishwashing detergent is dosed directly onto the absorbing devicefor about 0.1 to 0.5 seconds. The absorbing device, and consequently the undiluted detergent composition, is then contacted individually to the surface of each of the soiled dishes to remove said soiling. The absorbing device is typically contacted with each dish surface for a period of time range from 1 to 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish. The contacting of the absorbing device to the dish surface is preferably accompanied by concurrent scrubbing. EXAMPLES

The following compositions in accord with the invention were prepared.

% bv weight

I π III IN V NI

C12/13 alkyl ethoxy (ave. 25.5 21 18 23 20.0 3.7

2.2) sulphate

C12/14 Alkyl - - 2.0 - 7.0 5 polyglucoside 600

C12/14 alkyl amine oxide 5.5 1.6 2.1 4.0 2.0 -

C 12/14 alkyl di methyl - - 1.3 1.6 - 1.0 betaine

CIO Alkyl Ethoxylate - - 3.7 4.4 - 3.0

(ave. 8)

C12 alkyl N-methyl 5.5 7.0 8.0 4 - - glucamide

Cl l Alkyl Ethoxylate (ave. 0.9 1.5 - - 3.8 -

9)

Mg^"*^"4" ion 0.7 0.65 0.6 0.7 0.3 -

Cation 0.35 0.1 - - - -

Sodium cumene sulphonate 11.0 13 11.5 15 18 ii.:

Calcium xylene sulphonate 3.4 - - - - -

Lipolase(TM) 0.05 - 0.1 - -

The compositions are prepared by mixing all of the surfactants with the exception of the glucamide. The magnesium/ calcium salts are then pre-dissolved into solution together with the maleic acid and added to the surfactant mixture with the remaining components. Finally the pH was trimmed to 7.3 using hydrochloric acid.

Claims

1. A dishwashing detergent composition comprising a surfactant system, said system comprising a polyhydroxyfatty acid amide and/or a alkylpolysaccharide or mixtures thereof and, greater than 11%> hydrotrope selected from lower alkyl aryl sulphonate salts, C6-C12 alkanols, Ci-Cg carboxylic sulphate or sulphonate salts, urea, C1-C4 hydrocarboxylates, C1-C4 carboxylates and C2-C4 diacids and mixtures thereof.

2. A composition according to Claim 1, wherein said composition comprises at least 25%) active ingredients.

3. A composition according to either of the preceding claims, wherein said composition is in the form of a liquid or a gel.

4. A composition according to any of the preceding claims, wherein said composition comprises from 11.5% to 40%ι of said hydrotrope.

5. A composition according to any of the preceding claims, wherein said composition comprises from 1% to 30% of said alkylpolysaccharide.

6. A composition according to any of the preceding claims, wherein said composition comprises from 1% to 20% of said polyhydroxy fatty acid amide.

7. A composition according to any of the preceding claims, wherein said hydrotrope is selected from sodium cumene sulphonate, calcium xylene sulphonate, sodium toluene sulphonate or mixtures thereof.

8. A composition according to any of the preceding claims, wherein said surfactant system further comprises surfactants selected from anionic, nonionic and zwitterionic surfactants .