GB2292562A - Liquid Detergent Compositions - Google Patents

Abstract

Liquid detergent compositions comprising one or more anionic or nonionic surfactants or mixtures thereof selected from alkyl or hydroxyalkyl alkoxylated sulphates, detersive sulphonates, alkylpolysaccharides and polyhydroxy fatty acid amides and an amine oxide mixture. The amine oxide mixture comprises a C7 - C9 hydrocarbyl amine oxide mixed with a C12 - C14 hydrocarbyl amine oxide. The composition may also contain a betaine, an alkyl carboxylate or an alkyl ethoxy carboxylate. Calcium or magnesium compounds may also be present.

Description

LIQUID DETERGENT COMPOSITIONS J. M. Clarke P. R. Foley D. L. Strauss J. M. Vandermeer K. W. Willman Technlcal Fleld of the Invention The present invention relates to liquid detergent compositions, particularly to dishwashing compositions comprising a combination of long and short chain length amine oxides which exhibit improved ease and rate of soil removal.

Background of the Invention The types of soils commonly encountered in the a dishwashing load are often, although not exclusively derived from food. Non food derived soils which are often found include, for example lipstick and nicotine. The soils which are the hardest to remove are usually greasy soils. Particularly difficult soils to remove are those which have been baked-on or burnt-on or soils which have been allowed to harden onto the dish article.

Current dishwashing compositions are capable of the removal of the above mentioned soils. However, the consumer frequently has to apply some manual force in order to completely remove all the traces of particularly strongly adhering soils.

Thus, the aim of the present invention is to formulate a dishwashing composition which facilitates the removal of strongly adhering soils quickly and with minimal manual effort.

It has now been found that this objective can be achieved by the combination of certain surfactants and an amine oxide mixture comprising amine oxides having a C12-14 hydrocarbyl group in combination with amine oxides having a C79 hydrocarbyl group.

Numerous exemplary disclosures exist of amine oxides in detergent compositions. For example GB 1082 076 discloses liquid detergent compositions comprising alkyl polyethylene glycol ether sulphates and C10-C16 amine oxides.

US 5 164 117 discloses surfactant mixtures comprising substantially linear C6 24 amine oxides, fatty acid alkanolamide and alkyl sulphate. C8, C 1 2 and C 1 4 amine oxides are mentioned. US 5 164 118 discloses surfactant mixtures comprising substantially linear C6 24 amine oxides, alkyl sarcosinates and alkanolamides. US 5 164 120 discloses surfactant mixtures comprising substantially linear C6 24 amine oxides and alkylamidopropyldimethylbetaines.

EP-560570 discloses dishwashing detergent compositions comprising anionic and nonionic surfactants and amine oxides, specifically coco and lauryl amine oxides.

RD-338023 discloses dishwashing compositions comprising anionic surfactants such as AES and amine oxides. C12 and C14 amine oxide are specifically disclosed, but not C8 amine oxide.

However, none of the published prior art documents specifically disclose the combination of Cl2-l4 amine oxide with C79 amine oxide with alkyl ethoxy sulphate, detersive sulphonates, alkylpolysaccharides or polyhroxyfatty acid amides.

Unpublished European Patent Application Number 93202186 discloses liquid detergent compositions comprising short chain surfactants including C6-C1o amine oxides and C14 amine oxides and C12 or C16 amine oxides.

Unpublished US Patent Application number 8187254 discloses dishwashing detergent compositions comprising C10-22 amine oxides and specified surfactants. C8 amine oxide is disclosed, but C12/14 amine oxides are not. Unpublished US Patent Application number 8187255 discloses low sudsing, spontaneous grease emulsifying detergent compositions comprising alkyl carboxylate and C 10-22 amine oxide. C8 amine oxide is specifically disclosed, but C12/14 amine oxides are not mentioned.Unpublished US Patent Application number 8187249 discloses low sudsing, spontaneous grease emulsifying detergent compositions comprising surfactants from a selected group and C10-22 amine oxide, wherein C12 and Cl6 amine oxides are specifically disclosed but not C14 amine oxide. C8 amine oxides are also specifically disclosed.

Summary of the Invention The present invention is a liquid detergent compositiori comprising from 0.5% to 50% of one or more anionic or nonionic surfactants and mixtures thereof selected from C1 1 -C24 detersive sulphonates, C1 l-C24 alkyl or hydroxyalkyl alkoxylated sulphates having from 1 to 15 alkoxy groups, alkylpolysaccharides and polyhydroxy fatty acid amides and from 0.1% to 20% of an amine oxide mixture, wherein said amine oxide mixture comprises a first amine oxide according to the formula R 1 R2R3N--O, wherein R1 and R2 are independently C1-C3 alkyl or hydroxy alkyl groups and R3 is a C7-Cg hydrocarbyl group in combination with a second amine oxide according to the formula R4RsR6N--O wherein R4 and R5 are independently C1-C3 alkyl or hydroxyalkyl groups and R6 is a C 12-C 14 hydrocarbyl group and mixtures thereof.

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

Detailed Descnption of the Invention The present invention is a detergent composition comprising one or more anionic or nonionic surfactants or mixture thereof and a mixture of amine oxides.

Thus an essential ingredient according to the present invention is an amine oxide mixture. According to the present invention the amine oxide mixture comprises a first amine oxide according to the formula RlR2R3N- 0, wherein R1 and R2 are independently C1-C3 alkyl or hydroxy alkyl groups and R3 is an hydrocarbyl group having an average carbon chain length of C7-C9. Said first amine oxide is in combination with a second amine oxide according to the formula R4RsR6N-O wherein R4 and R5 are independently C 1 -C3 alkyl or hydroxyalkyl groups and R6 is a C12-Cl4 hydrocarbyl group and mixtures thereof. Preferably R1, R2, R4 and Rs are methyl groups.R3 is preferably an alkyl group with an average carbon chain length of 8. More preferably R3 is a linear C8 alkyl group, although it may exhibit a degree of branching. Preferably the ratio of said first amine oxide to said second amine oxide is from 100:1 to 1:100 more preferably from 50:1 to 1:50, most preferably from 10:1 to 1:10.

The present invention comprises from 0.1% to 20%, preferably from 0.5% to 15%, more preferably from 1% to 15% of said amine oxide mixture. Preferalby said amine oxide mixture comprises from 1% to 99%, more preferably from 5% to 90% of said first amine oxide.

According to the present invention the detergent composition comprises as an essential feature from 0.5% to 50%, preferably from 5% to 35%, most preferably from 10% to 25% of one or more of an anionic or nonionic surfactant or mixtures thereof selected from C 11 -C24 detersive sulphonates, C 11 -C24 alkyl or hydroxy alkyl alkoxylated sulphates having from 1 to 15 alkoxy groups, alkylpolysaccharides and polyhydroxy fatty acid amides. Preferably said surfactant - is selected from alkyl or hydroxyalkyl sulphate and detersive sulphonates and mixtures thereof.

According to the present invention suitable alkyl or hydroxyalkyl alkoxylated sulphates for use herein are of the formula RO(A)mSO3M, wherein R is an unsubstituted Cl 1-C24 alkyl or hydroxyalkyl component, preferably a C 1 2-C20 , alkyl or hydroxyalkyl, more preferably a C 12-Cl 8 alkyl or hydroxyalkyl component, A is an ethoxy or propoxy group, m is from 1 to 15, more preferably from 1 to 10, and M is H or a cation which may be selected from metal cations such as sodium, potassium, lithium, calcium, magnesium, ammonium or subsituted ammonium.Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations such as tetramethyl-ammonium, dimethyl piperidium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are C 12-C 18 alkyl polyethoxylate (2.25) sulphate, C12-Cl8 alkyl polyethoxylate (3) sulphate and C12-Cl8 alkyl polyethoxylate (4) sulphate wherein M is selected from sodium or potassium. C12-Cl4 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.

According to the present invention the compositions comprise from 5% to 50%, preferably from 5% to 35%, most preferably from 10% to 25% of said alkyl alkoxylated sulphate.

As used herein the term detersive sulphonates refers to the salts (e.g.

alkali metal and ammonium salts) of C 11 -C24, preferably C 1 2-C20 linear alkylaryl sulphonates, particularly linear alkyl benzene sulphonates, primary or secondary alkane sulphonates, alkene sulphonates such as aolefin sulphonates, ether sulphonates, sulphonated polycarboxylic acids, oxyalkane sulphonates (fatty acid isethionates), acylamino alkane sulphonates (taurides), alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof.

Preferred alkyl sulphonates for use herein are C12-Cl8 sodium paraffin sulphonates and C1 2-Cl 8 linear alkyl benzene sulphonates.

According to the present invention the detergent composition may comprise from 5% to 50%, preferably from 10% to 25% of said detersive sulphonate.

According to the present invention suitable alkylpolysaccharides for use herein may be nonionic alkylpolysaccharides or the corresponding sulphated polysaccharides and mixtures thereof. Alkylpolysaccharides suitable 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 11 to about 30, more preferably 11 to 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: R20(CnH2nO)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 0 to 3 preferably 2 to 3, t is from 0 to 10, preferably 0, xis 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.

According to the present invention the dishwashing compositions comprise from 0.5% to 50%, preferably from 1% to 30%, more preferably from 1.5% to 20% of said alkylpolysaccharide surfactant.

According to the present invention suitable polyhydroxy fatty acid amides for use herein are according to the formula

wherein R 1 is H, a C1 C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, preferably a Cl C4 alkyl, more preferably a C1 or C2 alkyl, most preferably a C1, and R2 is a Cs-C31 hydrocarbyl, preferably straight chain C7-C lg alkyl or alkenyl, most preferably straight chain C1 1- C1 7 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 corn 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- 1 -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 monosaccharide. Most preferred are the glycityls wherein n is 4, particularly CH2(CHOH)4CH2OH.

According to the formula R1 can be for example, Methyl, Nethyl, 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 l-deooxyglycityl, 2-deoxyfructityl, 1 -deoxymaltityl, l-deoxylactityl, 1deoxygalactityl, l-doexymannityl, 1 -deoxymaltotriotityl, etc.

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

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 lS, 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 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, Cl-Cs alkyl, and -C(O)R4-, wherein R4 is Cl-C2l 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)5-, -(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)2-0-(CH2)3 -, -(CH2)2-O-(CH2)3 -O-(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)CH2NM-(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 corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized 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(CHOR1)(CHOH)-CH20H, 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-CH20H.

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-C1 1 alkyl or alkenyl, most preferably straight chain Cs-Cg 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: CR3 (CH2)6C(O)N[CH2(CHOH)4CH2OH]-(CH2)2- [CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-(CH2)2- [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3; CH3 (CH2) 1 0C(O)N[CH2(CHOH)4CH20H]-(CH2)2- [CH2(CHOH)4CH20H]NC(O)(CH2)1oCH3; CH3 (CH2)8C(O)N[CH2(CHOH)4CH2OH] -(CH2)2-O-(CH2)2-O-(CH2)2- [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3; CH3(CH2)8C(O)N[CH2(CHOH)4CH20H]-CH2CH(CH3)(CH2)3- [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3; CH3(CH2)8C(O)N[CH2(CHOH)4CH2OH]-(CH2)3-O-(CH2)2-O-(CH2)3- [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3; CH3 (CR2)3 CH(CH2CH3 )C(O)N[CH2(CHOH)4CH2OH] -(CH2)2- [CH2(CHOH)4C H20H]NC(O)CH(CH2CH3 )(CH2)3 CH3 ; ; CH3(CH2)6C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-0-(CH2)3- [CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-(CH2)3-0-(CH2)2-0-(CH2)3- [CH2(CHOH)4CH20H]NC(O)(CH2)8CH3; C6HsC(O)N[CH2(CHOH)4CH2OH]-(CH2)3-O-(CH2)2-O-(CH2)3- [CH2(CHOH)4CH2OH]NC(O)C6Hs; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H1-(CH2)2- [CH2(CHOH)4CH2OH]NC(O)(CH2)8CH3.

These compounds can be readily synthesized from the following sugar diamines: HN[CH2(CHoH)4CH20H]-(CH2)2- [CH2(CHOH)4CH20H]NH; HN[CH2(CHOH)4CH2 OH] - CH2CH(CH3 )(CH2)3 - [CH2(CROH)4CH2OH]NH; HN[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-(CH2)2- [CH2(CHOH)4CH20H1NH; HN[CH2(CHOH)4CH2 OH] -(CH2)3 -O- (CH2)2-0-(CH2)3 -[CH2(CHOH)4CH20H]NH; and HN [CH2(CHOH)4CH2 OH] -(CH2)3 - [CH2(CHOH)4C H20H]NH.

The compositions according to the present invention comprise from 0.1% to 30% , preferably from 1% to 20%, most preferably from 3% to 10%, of said poly hydroxy fatty acid amide.

According to the broadest aspect of the present invention the detergent composition may comprise a number of optional ingredients such as additional surfactants, builders, chelants, soil release agents, antiredeposition agents, polymeric dispersing agents, bleaches, enzymes, calcium and magnesium ions, brightener, perfumes and dyes.

Suitable optional surfactants for use herein include other anionic, nonionic, cationic, amphoteric and zwitterionic surfactants and mixtures thereof.

Anionic surfactant Anionic surfactants suitable for use herein may be essentially any anionic surfactant, including anionic sulphate or carboxylate surfactant.

Anlomc sulphate surfactant The anionic sulphate surfactant may be any organic sulphate surfactant. 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.

Other suitable anionic surfactants for use herein include C9-C 17 acyl N-(C 1-C4 alkyl) glucamine sulphate.

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 C12 to C16 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 C13 or less, and the average x is from 3 to 6 when the average R is greater than C13, and M is a cation, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono, di-, and triethanol-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.

Anlomc alkyl polyethoxy polycarboxylate surfactant Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula:

wherein R is a C6 to C18 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 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 O 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 8-12.

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-C1 0, preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R5 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)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.

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 trialkanolammonium, and Cl-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 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, alkyl succinates and sulphosuccinates, monoesters of sulphosuccinate (especially saturated and unsaturated C 12-Cl 8 monoesters) diesters of sulphosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl C6.20 sarcosinates. 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).

Compositions according to the present invention comprise at least 3%, preferably from 3% to 40%, most preferably from 3% to 30% of said anionic surfactants.

Nonionic surfactant Suitable nonionic detergent surfactants for use herein include nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols and nonionic fatty acid amides. According to the present invention the compositions may comprise from 0% to 30%, preferably from 0.1% to 25%, more preferably from 0.5% to 20% of said nonionic surfactants.

Nonionic condensates of alkyl phenols The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. 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.

Nonlonle ethoxylated alcohol surfactant The 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 11-C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12-C 14 primary 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-C1 5 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), NeodolTM 457 (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), NeodolTM23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethyene oxide) marketed by Shell Chemical Company, KyroTM EOBN (the condensation product of C 13-Cl 5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, 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 with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Nonionic EO condensation products with propylene oxide/ethylene diamineadducts 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 TetronicTM compounds, marketed by BASF.

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

wherein R is a C8-Cl8 alkyl group, and Ri is of the general formula:

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 10 to C 14 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 amphodicarboxylic acid for use herein ins the amphoteric surfactant Miranol(TM) C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

Amme oxide surfactant According to the present invention in addition to the essential C79 and C 12-14 amine oxide ingredient, other amine oxides useful as amphoteric surfactants may be used herein. Such optional but highly preferred amine oxides suitable for use have the formula:

wherein R7 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 10 to 20 carbon atoms, preferably 10 to 14 carbon atoms; and R8 and Rg are independently C1 3 alkyl or C23 hydyroxyalkyl groups, or a polyethylene oxide group containing from 1 to 3, preferably 1, ethylene oxide groups.These amine oxide surfactants in particular include C1 0-C 14 alkyl dimethyl amine oxides and C10-Cl2 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include diethyldecylamine oxide, bis-(2hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide and dodecylamidopropyl dimethylamine oxide.

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

Betake surfactant According to the present invention the compositions may thus comprise betaines. The betaines useful, as zwitterionic surfactants, in the present invention are those compounds having the formula R(R')2N+R2COO- wherein R is a C6-C 18 hydrocarbyl group, preferably a C10-C16 alkyl group or C 10-16 acylamido alkyl group, each R1 is typically C 1 -C3 alkyl, preferably methyl, and R2 is a C1-Cs hydrocarbyl group, preferably a C1-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[C 14-16 acylmethylamidodiethylammonio]- 1 -carboxybutane; C 16- 18 acylamidodimethylbetaine; C 12- 16 acylamidopentanediethylbetaine;[C12-16 acylmethylamidodimethylbetaine. Preferred betaines are C 12- 18 dimethyl-ammonio hexanoate and the C 1 o 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.

The complex betaines suitable for use herein have the formula:

wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, preferably 12 to 14 carbon atoms, A is the group (C(O)), n is 0 or 1, R1 is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer ofO 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.

According to the present invention the composition may comprise from 0% to 10%, preferably from 0% to 5% of said betaines.

Sultaines The sultaines useful in the present invention are those compounds having the formula (R(R1 )2N+R2SO3- wherein R is a C6-C 18 hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a C12-Cl3 alkyl group, each R1 is typically C1-C3 alkyl, preferably methyl, and R2 is a C 1 -C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group.

The zwitterionics herein above may also be present in small quantities so as 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 enzymes, proteolytic enzymes and amylolytic 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 stabilising system.

Liquid dishwashing compositions according to the present invention may comprise any of the ingredients listed herein above. In addition the dishwashing compositions may comprise other ingredients such as bleaches, bactericides, anti-tarnish agents, chelants, suds enhancers, opacifiers, solvents, hydrotropes, calcium and magnesium ions and perfumes and dyes.

Hydrotropes A hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0% to 40%, preferably from 1% to 15%, by weight.

Useful hydrotropes include sodium, potassium, calcium and ammonium salts of xylene sulphonates, toluene sulphonate and cumene sulphonate and mixtures thereof. Other compounds useful as hydrotropes herein include polycarboxylates and urea. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties.

An example of a commercially available alkylpolyethoxy polycarboxylate which can be employed herein is POLY-TERGENT C, Olin Corporation, Cheshire, CT.

Another compound useful as a hydrotrope is alkyl amphodicarboxylic acid of the generic formula: (CH2)x COO RCNHCH2CH2N < (CH2)x COOM wherein R is a C8 to C18 alkyl group, x is from 1 to 2, 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 alkyl chain length (R) is a C 10 to C 14 alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.

A suitable example of an alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol R 2CM Conc. manufactured by Miranol, Inc., Dayton, NJ.

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 1% 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:

wherein R is an alkyl, alkenyl, or alkyl aryl group having from l 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 1(2-n-butoxy-1-methylethoxy)propane-2-ol (n=2), and mixtures thereof.

Other solvents useful herein include the water soluble CARBITOL or CELLOSOLVE solvents. These solvents are compounds of the 2-(2alkoxyethoxy)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-1,3-pentanediol. The low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.

The alkane mono and diols, especially the Cl-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 C1-C4 dihydric alcohols, including propylene glycol, are also preferred.

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

Calcium Compositions according to the present invention may optionally comprise from 0.01% to 3%, more preferably from 0.15% to 0.9% of calcium ions. It has been found that the presence of calcium greatly improves the cleaning of greasy soils for compositions containing polyhydroxy fatty acid amide. 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 In order to provide good product stability, and in particular to prevent the precipitation of insoluble calcium salts malic, maleic or acetic acid, or their salts, or certain lime soap dispersant compounds may be added to the composition of the present invention comprising calcium . Where calcium is present, malic, maleic or acetic acid, or their salts can be added at levels of from 0.05% to 10% of the composition and a molar ratio with calcium offrom 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 neutralisation 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 neutralized surfactant salts and the hydrotrope are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.

pH of the compositions The compositions according to the present invention formulated for use in manual dishwashing applications are preferably formulated to have a pH at 200C of from 3 to 12, preferably from 6 to 9, most preferably from 6.5 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 form 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.

Liquid compositions According to the present invention the detergent compositions 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 Cl -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.

Examples 1-6 The following liquid compositions of the present invention are prepared by mixing the listed ingredients in the given amounts.

% by weight of the total composition 1234567 C12/13 alkyl ethoxy sulphate 17 14 5 10 1.5 5 25 C 12 sodium paraffin sulphonate - - 15 - - - C12/14 alkylpolyglucoside 600 1.8 - - - - - C 12 linear alkyl benzene sulphonate - - 6 - - - C8 alkyl sulphate - - - - 7 2 C12/14 alkyl amine oxide 2 2 1 2 0.5 0.5 3.0 ave.C8 alkyl amine oxide 7 9 0.5 12 2 1.5 2.0 C12/14 alkyl di methyl betaine 0.5 - 2 - - - - C12 alkyl N-methyl glucamide - 5 10 12 0.5 0.5 5.0 C10 alkyl ethoxylate (ave. 8) 5 1 - 5 - - 1.0 C8 alkyl ethoxylate (ave. 0.6) - - - - 10 - isopentadecanoic acid - - 5 - - - - C12/14 alkyl ethoxy carboxylates 2.0 - - - - - - Mug++ ion 0.5 - 0.3 0.6 - - 0.6 Cay lion 0.3 0.15 0.1 - - - 0.3 Maleic acid - 0.2 0.3 - - - 2.0 Citric acid - - - - - 6 MiranolR - 2 - - - - - Butyl Carbitol - - - - - 3 Butoxypropylpropanol - - - - - 8 Sodium hydroxide - - - - 0.7 0.6 Sodium cumene sulphonate 1.4 12 2 10 - - 3.0 Lipase - - 0.015- - - - 1234567 Amylase - - 0.01 - - - Protease - - 0.05 - - - - NeodolR23-3 - - - - 4 - - Minors up to 100%

Claims (10)

1. CLAIMS 1. A liquid detergent composition comprising from 0.5% to 50% of one or more anionic or nonionic surfactants or mixtures thereof selected from C11-C24 detersive sulphonates, C11-C24 alkyl or hydroxyalkyl alkoxylated sulphonates having from 1 to 15 alkoxy groups, alkylpolysaccharides and polyhydroxy fatty acid amides, and from 0.1% to 20% of an amine oxide mixture, wherein said amine oxide mixture comprises a first amine oxide according to the formula R1R2R3N-O, wherein R1 and R2 are independently C1-C3 alkyl or hydroxy alkyl groups and R3 is a C7-Cg hydrocarbyl group in combination with a second amine oxide according to the formula R4RsR6N-O wherein R4 and R5 are independently C1-C3 alkyl or hydroxyalkyl groups and R6 is a C 12-C 14 hydrocarbyl group and mixtures thereof.
2. 2. A liquid detergent composition according to claim 1, wherein the ratio of said first amine oxide to said second amine oxide is from 100:1 to 1:100.

   3. A liquid detergent composition according to either of claims 1 and 2, wherein said amine oxide mixture comprises from 1% to 99% of said first amine oxide.
3. 3. A liquid detergent composition according to any of the preceding claims, wherein said surfactant is selected from an alkyl or hydroxyalkyl alkoxylated sulphate and detersive sulphonates and mixtures thereof.
4. 4. A liquid detergent composition according to any of the preceding claims, comprising from 5% to 35% of said alkyl or hydroxyalkyl alkoxylated sulphate.
5. 5. A liquid detergent composition according to any of the preceding claims, wherein R1 and R2 are methyl groups and R3 is a C8 hydrocarbyl group.
6. 6. A liquid detergent composition according to any of the preceding claims comprising from 1% to 15% of said amine oxide mixture.
7. 7. A liquid detergent composition according to any of the preceding claims, further comprising a polyhydroxy fatty acid amide.
8. 8. A liquid detergent composition according to any of the preceding claims, further comprising C12-Cl4 alkyl betaines.
9. 9. A liquid detergent composition according to any of the preceding claims, further comprising C11-16 alkyl carboxylates and/or a C12-l6 alkyl ethoxy carboxylate or mixtures thereof.
10. 10. A liquid detergent composition according to any of the preceding claims, further comprising magnesium or calcium ions or mixtures thereof.