CA2191136C - Manual dishwashing compositions - Google Patents

Abstract

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

Description

WO 95/30729 ~ PCT/US95/05069 21~1i36 MANUAL DISHWASHING COMPOSITIONS
Technical field of the Invention The present invention relates to dishwashing detergent compositions comprising high levels of hydrotropes.
Backeround 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 dishwashing 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 surface 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.

2i9113b 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 WO 95/30729 ~ PCT/US95105069 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

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.
Summar,~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, alkanols, C 1-C6 carboxylic sulphate or sulphonate salts, urea, C 1-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 Hvdrotropes WO 95/30729 ~ PCTIUS95/05069 2~9i136 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, C6-C 12 alkanols, C 1-C6 carboxylic sulphate or sulphonate salts, urea, C 1-C4 hydrocarboxylates, C 1-C4 carboxylates and C2-C4 diacids and mixtures thereof.
Suitable lower alkyl aryl sulphonates are preferably C~-Cg 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 C 1-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 CZ-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 C6-C 12 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%, 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 alkylpolyglyc.osides have the formt:la:
R20(CnH2n0)t(gly~osyl~
wherein RZ is selected from the group c~~nsisting of alkyl, alkylphcnyl, hydraxyatkyl, hydroxyalkytphenyl, and mixtures thereof in ~which the aliryl groups contain from 10 to 8, preferably from 12 to 1~, carbon ata:ns; n is 2 ar 3, preferabiy from about 1.3 to about 3, vast preferably frart about 1.3 to at~out 2.7. x is from 1.0 to 10, preferably front 1.0 to 3, frost preferably fi'a:n 1.3 to ~.7 The glycosyl is preferably derived from glucose. To prepare these compounds. tl:e alcohol or alkylpolyetho~cy alcohol is formed first and then reacted with glucose, or a source of glucose, to ferrn the gluc;eside (attachment at ttse 1-positionj. The additional glyeos511 unis car then be attached between their J-positicri and the preceding ,~lycosyl units 2-,3-, ~- and~'or 6-position, prefer ably predominantly the 2-position. In additiea to the polysacc~tarides mentioned obey ~ tha carrespondirg sulphated pc!ysaoct~~arides tray xlxo he used 1~.erein.
According to the present in~~e.~.tion the dislswashing cvmpasitions comprise from 0°.o to 50%, preferably tom 1°ro to 30°~0, mare preferably from 1.5% to ?G% ot= said aiky'polysaccharide surfactant Po~yll, d~ r~_x_v_ fatty acid a:~~id~ 5tarfa~an~
Poly hydroxy fatty arid amides suitable for use herein are acecrdir;g to the formula:
R~-~ ~l-Z

wherein R1 is H, a C2_C~ hydracarbyl, 2-hydraxy ethyl, 2-hydroxy propyl or mixtures thereof pre:erably a CI-C4 aii:yl, r<:are preferably a C1 ar C:2 alkyl, most preferably a C1~ ~d R2 is a CS-C31 hydrocarbyl, preferably- straight cram C7-Cig alkyl or alkenyl, most ~referahly strail;ht cEtain C11-C1y alkyl ar alkenyl or mixtures thereof;
and Z is a polyhydrocarbyl having a linear hydrocarbyl chain with at Ieast 3 hydroxyl groups directly connected to the ;;rain ar an alkov,:ylated cler;vative thereof. Z is preferably derived from a reducing sugar ira redyactive amination reaction: more preferably Z is a glycityl. Suitable reducing sugars inciuda blucose, fruc.'tese, maltase, lactose, galactose, mattnose and xylose. As raw materials high d.extrese corn syn:p, high fructose com syrup and ?'tip;h tt~~altose corn syrup can be utili>ed as wel! as individual sugars listed above, It should be tandarstood that these corn syrups may yield a mixture of sugar components fur Z. Z is preferably selected from the group consisting ef WO 95/30729 . PCT/US95/05069 -CH2(CHOH)nCH20H, -CH(CH201-i)-(CHOH)n-1-CH20H, or -CH2-(CHOH)2(CHOR')(CHOH)-CH20H and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 inclusive and R' is hydrogen or a cyclic or aliphatic monosaccharide.
Most preferred are the glycityls wherein n is 4, particularly CH2(CHOH)4CH20H.
According to the formula R1 can be for example, N-methyl , N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. RS-CO-N< can be for example cocamide, stearimide, oleamide, lauramide, myristamide, capricamide, palmitamide, talloamide etc. Z cacti 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 v =0 I t 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 1 S 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 R2 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 R2 is independently selected from C2-Cg branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or combinations thereof), m is an integer from 1 to about 5, and R3 is selected from hydrogen, C 1-CS alkyl, and -C(O)R4-, wherein R4 is C 1-C21 alkyl, including -C(O)R. The X moiety may be derived from commercially available amine compounds such as, for example, JeffaminesR
(supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230 and J-D400.
Preferred X moieties therefore include: -(CH2)2-, -(CH2)3-, -(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'O'(CH2)2-~ -(CH2)2-~-(CH2)2-~'CH2)3-~-(CH2)3-~ -(CH2)2-~'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-~(C6H4)~-(CH2)2-~ -(CH2)3-~(C6H4)~OCH2)3-~ -(CH2)2-NHCH2(C6H4)CH2~-(CI"i2)2-~ -(CH2)3-NHCH2(C6H4)CH2~-(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 corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilised as well as the individual sugars listed above. These corn 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-CH20H, -CH(CH20H)-(CHOH)p_ 1-CH20H, -CH2-(CHOH)2(CHORI)(CHOH)-CH20H, where p is an integer from 1 to 5, inclusive, and RI
is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof.. Most preferred are glycityls wherein p is 4, particularly -CH2-(CHOH)4-CH20H.
Preferred R and R' groups are independently selected from C3-C21 hydrocarbyl moieties, preferably straight or branched chain C3-C 13 alkyl or alkenyl, more preferably straight chain C5-C 11 alkyl or alkenyl, most preferably straight chain CS-Cg alkyl or WO 95/30729 . : ; PCT/US95/05069 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)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3 (CH2) 1 OC(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2) 1 OCH3 CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3; CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)3CH(CH2CH3)C(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)CH(CH2CH3)(CH2)3CH3;
CH3(CH2)6C(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
C6HSC(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NC(O)C6H5; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3.
These compounds can be readily synthesised from the following disugar diamines:
HN[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-(CH2)2-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NH;
and HN[CH2(CHOH)4CH20H]-(CH2)3-[CH2(CHOH)4CH20H]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 s stem WO 95/30729 ~ PCT/US95/05069 2 ~ 9, ~ 13 0 io 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 su~hate surfactant The anionic sulphate surfactant may be any organic sulphate surfactant. It is preferably selected from the group consisting of C 10-C 16 alkyl sulphate which has been ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per molecule, C9-C 17 acyl-N-(C 1-C4 alkyl) glucamine sulphated, -N-(C2-C4 hydroxyalkyl) glucamine sulphate, and mixtures thereof. More preferably, the anionic sulphate surfactant is a C 10-C 16 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 C 10-C 16 alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 12, ethylene oxide groups.
The C 10-C 16 alcohol itself is commercially available. C 12-C 14 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 Cg-C 17 acyl-N-(C 1-C4 alkyl) and -N-(C 1-C2 hydroxyalkyl) glucamine sulphates, preferably those in which the Cg-C 17 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.

- WO 95/30729 ~ ~ ~ ' ; ~ ~ PCT/US95/05069 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 Cg-C2p linear alkylbenzene sulphonates, Cg-C22 primary or secondary alkane sulphonates, Cg-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(CH2CH20)x CH2C00-M+ wherein R is a C 12 to C 16 alkyl group, x ranges from 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 13 or less, and the average x is from 3 to 6 when the average R
is greater than C 13, 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 al -1 nolyethoxy pol cay rboxylate surfactant Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include those having the formula:
R-O-(CH- CH- O)x-R3 wherein R is a C6 to C 1 g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic PCT/US95/05069 _.

acid radical, and mixtures thereof, wherein at least one R1 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 R3 CH(R4)COOM, wherein R3 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 RS-R6-COOM, wherein RS is C~-C 10, preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane.
(Note: RS
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)r,.l-(CHR)n-CH(COOM)(CHR)o-(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.

- WO 95/30729 PCTlUS95/05069 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 C 1-CS 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-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-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-aryl 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(CH2CH20)kCH2C00-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.

j PCT/US95/05069 -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 TergitoITM
15-S-9 (the condensation product of C 11-C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12-C 14 Pnmary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14-C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12-C 13 linear alcohol with 6.54 moles of ethylene oxide), NeodoITM 45-7 (the condensation product of C 14-C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14-C 15 linear alcohol with 4 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C

linear alcohol with 3 moles of ethylene oxide) marketed by Shell Chemical Company, and KyroTM EOBN (the condensation product of C 13-C 15 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 glycol The condensation products of ethylene oxide (EO) with a hydrophobic base formed by the condensation of propylene oxide (PO) with propylene glycol are suitable 2i 91 136 for use herein. Examples of compounds of this type include certain of the commercially-available PluroniG~M surfactants, marketed by BASF.
Iy'onio~nic EO condensation B~~oduc~ith urqpyle a oxidelethvle a dia 'pe acts 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 TttronicT~'i compounds, marketed by BASF.
According to the present invention the dishwashing compositions may comprise nom 0°~o to 30%, preferably from 0.1°ii; to 25'/0. rr~ore preferably from 0.5% to 20% of said nonionic surfactants.
Am~tt~teri~surfa Suitable amphoteric surfactants for use herein include the all'yl amphocarboxylic acids of the formula:
C
RC-NHCH2CH2Ri wherein I~ is a Cg-Clg alkyl group, and Ri is of the general formula FIL)xCOC- ~H2)xC00-N or ''~+)-CF'l2CH20H

R
wherein R1 is a (CH2)xC00hi or CH2CHZOI~, and x is 1 or 2 and M is preferabiy 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 C10 to Clq, alkyl group. A preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the arnphodicarboxylic 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) ~.2M Conc. 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 vvention include those compounds having the formula O
R3 (OR4)xN(RS )2 wherein R3 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 hydrox~~alkylene 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 RS 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 RS 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 C 10-C 1 g alkyl dimethyl amine oxides and Cg-C 12 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 l0-C 1 g alkyl dimethylamine oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactant WO 95/30729 ' ; PCT/US95/05069 Zwitterionic surfactants can also be incorporated into the detergent compositions herein.
Betaine surfactants According to the present inventior the compositions may comprise betaines. The betaines useful as zwitterionic surfactants in the present invention are those compounds having the formula R(R1)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group, preferably a C 1 p-C 16 alkyl group or C 1 p_ 16 acylamido alkyl group, each R1 is typically C 1-C3 alkyl, preferably methyl, and R2 is a C 1-CS hydrocarbyl group, preferably a C 1-C3 alkylene group, more preferably a C 1-C2 alkylene group. Examples of suitable betaines include coconut acylamidoprops idimethyl betaine; hexadecyl dimethyl betaine;
C12-14 acylamidopropylbetaine; Cg_l~, acylamidohexyldiethyl betaine; 4[C14-16 aeylmethylamidodiethylammonio]-1-carbo~..ybutane; C 16-18 acylamidodimethylbetaine;
C12-16 acylamidopentanediethyl-betaine; [C12-16 acylmethylamidodimethylbetaine.
Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18 acylamidopropane (or ethane) dimethyl (oT diethyl) betaines.
The complex betaines for use herein have the formula R - (A)n - ~ - (C~1)x]y - N - Q (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, R1 is hydrogen or a lo~rer 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 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 C6-C 1 g hydrocarbyl group, preferably a C 10-C 16 alkyl group, more preferably a C 12-C 13 alkyl group, each R 1 is typically C 1-C3 alkyl, preferably methyl, and R2 is a C 1-C6 hydrocarbyl group, preferably a C 1-C3 alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines include WO 95/30729 y:191 13 6 C 12-C 14 dimethylammonio-2-hydroxypropyl sulfonate, C 12_ 14 amido propyl ammonio-2-hydroxypropyl sultaine, C I 2-14 dihydroxyethylammonio propane sulfonate, and C 16-1 g dimethylammonio hexane sulfonate, with C 12-14 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 amyiases 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.

WO 95130729 ~. - PCT/US95/05069 ~~'~~1 ~Jb 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 C.A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). The LSDP is the % weight. ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025g of sodium oleate in 30m1 of water of 333ppm CaC03 (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.

.~ ~ X91 i 3 6 PCT/US95/05069 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, malefic 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, malefic 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.
Ma nesium 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 2191I3~
fans, which reduces corrosive properties The neutralised surfactant salts and the hydrotrope are then added to the f nil mixing tank and any optional ingredients are added before adjusting the pH.
Qreanic solvent The compositions of the im:enzic~n will mast preferably contain an organic solvent system present at levels of from I% to 30°I° by weight, preferably from 1% to 20% by weight, more preferably form 2°.~o to 15°~o by' weight of the composition. The organic solvent system may be a mono, or mL~ced solvent system; but is preferably in mixed solvent system. Preferably, at least the major component of ahe solaent system is of loin volatility. Suitable organic solvents for use herein has the general formula:

RO(CH2CH0)nH
wf~erein R is an alkyl, askenyl, or alkyl aryl group having from I to 8 carbon atoms, and n is an integer from 1 to 4. Prcferab:y, A is an alkyl group containing 1 to 4 carbon atoms, and n is I or 2. Especially preferred R groups ar a n-butyl or isobutyi.
Preferred solvents of this type are 1-n-butoxypropane-2-of (n=1); and 1(2-n-butoxy-1-methylethoxy)propane-2-of (n=Z), and mixtures thereof.
Other solvents useful herein include the water soluble C ARBrTOL or CELLOSOLV~ solvents. These solvents are compounds of the 2-(2-alkoxyethoay)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl.
Other suitable salv2nts are benzyl alcohol, and dials such as 2-ethy!-1,3-hexanediol and 2,2,4-trimethl-1,3-pentanediol.The low molecular weight, water-soluble, liquid polyethylene glycols are also suitable :~alvents for use herein.
The alkane mono and dials, especially the C 1-Cb alkane mono and dials are suitable for use herein. C I -C~ monohydric alcohols (ey ethanol, prapanol, isopropanot, butanol and mixtures thereof) are preferred, with ethanol particularly preferred. The C1-C4 dihydric alcohols, including prcpylene glycol, are also preferred.
T'hickg ing aagtL
TO'flL P . 0p4 WO 95/30729 ~ ' 2 ~ 91 7 3 6 pCT/US95/05069 The compositions according to the present invention may addditionally comprise thickening agents, such as polyquaterium cellulose cationic polymer, for example QuatrisoftR 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.
Deterrent compositions According to the present invention the compositions may be liquid or gel compositions.
Liauid 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 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 WO 95/30729 _ - ~ PCT/US95/05069 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 RVT 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 WO 95/30729 ' j ~ PCT/US95/05069 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 1 ml. 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 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 WO 95/30729 < ' PCT/US95/05069 21~11~6 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.

WO 95/30729 ~ j ~ i ~ 3 PCT/US95/05069 EXAMPLES
The following compositions in accord with the invention were prepared.
by weight I II III IV V VI
C 12/ 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.E 2.1 4.0 2.0 -C12/14 alkyl di methyl - - 1.3 1.6 - 1.0 betaine C 10 Alkyl Ethoxylate - - 3 .7 4.4 - 3.0 (ave. 8) C 12 alkyl N-methyl 5.5 7.0 8.0 4 - -glucamide C 11 Alkyl Ethoxylate (ave. 0.9 1. 5 - - 3 .8 -9) Mgr ion 0.7 0.6 ~ 0.6 0.7 0.3 -Ca~ion 0.35 0.1 - - - -Sodium cumene sulphonate 11.0 13 11.5 15 18 11.2 Calcium xylene sulphonate 3.4 - - - - -Lipoiase(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 malefic acid and added to the surfactant mixture with the remaining components.
Finally the pH was trimmed to 7.3 using hydrochloric acid.

Claims (8)

Claims:
1.

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 allcanols, C1-C6 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 claim 1, wherein said composition comprises from 11.5% to 40% of said hydrotrope.

5. A composition according to claim 1, wherein said composition comprises from 1% to 30% of said alkylpolysaccharide.

6. A composition according to claim 1, wherein said composition comprises from 1 % to 20% of said polyhydroxy fatty acid amide.

7. A composition according to claim 1, wherein said hydrotrope is selected from sodium cumene sulphonate, calcium xylene sulphonate, or mixtures thereof.

8. A composition according to claim 1, wherein said surfactant system further comprises surfactants selected from anionic, nonionic and zwitterionic surfactants.