WO1995020024A1

WO1995020024A1 - Detergent compositions

Info

Publication number: WO1995020024A1
Application number: PCT/US1995/000984
Authority: WO
Inventors: Joanna Margaret Clarke; Peter Robert Foley; Daniel Louis Strauss; James Michael Vander Meer; Kenneth William Willman
Original assignee: The Procter & Gamble Company
Priority date: 1994-01-25
Filing date: 1995-01-25
Publication date: 1995-07-27
Also published as: GB2288185A; GB9401321D0

Abstract

The present invention relates to detergent compositions comprising a poly hydroxy fatty acid amide and a C16-18 amine oxide which exhibit improved speed and ease of soil removal and are mild towards the skin.

Description

DETERGENT COMPOSITIONS

Technical Field of the Invention

The present invention relates detergent compositions, particularly to dishwashing compositions comprising a Ci6_ιg amine oxide which exhibit improved ease and rate of soil removal and improved mildness.

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, one 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.

However, it has been observed that many possible ingredients which would deliver the desired quick and easy removal of soils found on dishes, with minimal manual agitation, are often aggressive towards the human skin. Typically, this will result in the skin of the consumer becoming dry, which leads to roughness and chapping. In severe cases the ingredients may cause itchiness and skin rashes. It is believed that this effect is due to the ability of individual ingredients to remove the natural oils present on the skin.

Thus, it is a further object of the present invention to formulate a detergent composition, particularly a manual liquid dishwashing composition which facilitates the quick and easy removal of tough stains and is mild towards the skin.

It has now been found that these objectives can be achieved by the combination of certain surfactants, comprising a poly hydroxy fatty acid amide and an amine oxide having a C\ .\ hydrocarbyl group.

Numerous exemplary disclosures exist of poly hydroxy fatty acid amides in detergent compositions. For example WO 92/06159 discloses detergent compositions comprising poly hydroxy fatty acid amides and alkyl ester sulphonates. Further examples include US 5 164 117 which discloses surfactant mixtures comprising substantially linear Cg_24 amine oxides, 2 hydroxyethyl, fatty acid alkanolamide and alkyl sulphate. 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 amine oxide and lauryl amine oxide. RD-338023 discloses dishwashing compositions comprising anionic surfactants including alkyl ether sulphonates and amine oxides, C\ amine oxide is not specifically disclosed.

In addition amine oxides are also a known class of surfactants and are exemplified in US 5 164 117, US 5 164 118, US 5 164 120, EP-560 570 and RD 338028.

However, none of the published prior art documents specifically a disclose C 16-18 amine oxide or recognise its performance benefits or the performance benefits of the combination of a poly hydroxy fatty acid amide with a Cj _i8 amine oxide. More particularly, the art does not recognise the cleaning benefits that this combination can provide with certain other surfactants.

Unpublished European patent application number 93202186 discloses mixtures of C 12/ 14/ 16 amine oxides with short chain anionic surfactants. Poly hydroxy fatty acid amides are not disclosed.

Summary of the Invention

The present invention is a detergent composition comprising from 1 % to 99.9% of a poly hydroxy fatty acid amide, an amine oxide and optionally other surfactants and mixtures thereof. Said poly hydroxy fatty acid amide is according to the formula:

wherein R5 is a C5-C31 hydrocarbyl, 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, and R4 is H, a C1-.C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, and from 0.1 % to 99% of an amine oxide and optionally other surfactants, wherein said amine oxide is according to the formula R1R2R3N-O, wherein Ri and R2 are independently C1-C3 alkyl or C2- C3 alkyl hydroxy groups and R3 is an alkyl group having on average from 16 to 18 carbon atoms 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

The present invention is a detergent composition comprising a poly hydroxy fatty acid amide and a Ci6_ιg amine oxide.

Thus, an essential ingredient according to the present invention is a poly hydroxy fatty acid amide, according to the formula

R5-C-N-Z

O R4 wherein R4 is H, a Cj_C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof, preferably a C1-C4 alkyl, more preferably a C\ or C2 alkyl, most preferably a Ci, and R5 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, most preferably straight chain Cn-Cπ 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(CH₂OHMCHOH)n-l-CH₂OH, or -

CH2-(CHOH)2(CHOR')(CHOH)-CH2θH 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)4CH2θH.

According to the formula R4 can be for example, N-methyl , N- ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2- hydroxy propyl. R5-CO-N < can be for example cocamide, stearimide, oleamide, Iauramide, myristamide, capricamide, palmitamide, talloamide etc. Z can be 1-deooxyglycityl, 2-deoxyfructityl, 1-deoxymaltityl, 1- deoxylactityl, 1-deoxygalactityl, 1-doexymannityl, 1-deoxymaltotriotityl, etc.

Compositions according to the present invention comprise from 1 % to 99.9% , preferably from 1 % to 60%, most preferably from 3% to 50%, of said poly hydroxy fatty acid amide.

The other essential ingredient according to the present invention is an amine oxide. According to the present invention the amine oxide is of the formula R1R2R3N-O, wherein Ri and R2 are independently C1-C3 alkyl or C2-C3 alkyl hydroxy groups or mixtures thereof and R3 is an alkyl group having on average from 16 to 18 carbon atoms and mixtures thereof. Preferably Rj and R2 are methyl groups. R3 is preferably an alkyl group with an average carbon chain length of 16. More preferably R3 a linear C\ alkyl group, although it may exhibit a degree of branching.

The present invention comprises from 0.1 % to 99%, preferably from 0.5% to 20%, more preferably from 1 % to 15%, and most preferably from 3% to 10% of said amine oxide. 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, anti- redeposition agents, polymeric dispersing agents, suds supressor, bleaches, brightener, perfumes and dyes.

Suitable optional surfactants for use herein include 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, sulphonate or carboxylate surfactant.

Anionic sulphate surfactant

The anionic sulphate surfactant may be any organic sulphate surfactant. It is preferably a Cjo-Ci6 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 20 moles of ethylene oxide per molecule

Alkyl ethoxy sulphate surfactants suitable for use herein comprise a primary alkyl ethoxy sulphate derived from the condensation product of a C10-C16 alcohol with an average of from 0.5 to 20, preferably from 0.5 to 12, ethylene oxide groups. C12-C14 alkyl sulphate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.

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 _f respectively.

Other suitable anionic surfactants for use herein include C9-C17 acyl-N-(Cl-C4 alkyl) glucamine sulphate. Anionic sulphonate surfactant

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

Anionic alkyl ethoxy carboxylate surfactant

Alkyl ethoxy carboxylates suitable for use herein include those with the formula RO(CH2CH2θ)x CH2COO-M + wherein R is a C12 to C16 alkyl group, x ranges from O 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 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 Ci2 o Cj4 alkyl group.

Anionic alkyl polyethoxy polycarboxylate surfactant

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

R - O - (CH - CH - 0)x - R3

I I

Rl R₂

wherein R is a C to Cj alkyl group, x is from 1 to 25, Rj 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 Rj 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 R 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 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 R-5-R6-COOM, wherein R-5 is C⁷-C^, preferably C^-C^, alkyl or alkenyl and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane. (Note: R-5 can be in the ortho, meta or para position relative to the carboxyl on the ring.)

C. Still another class of secondary soaps comprises secondary carboxyl compounds of the formula CH3(CHR)k-(CH2)_m-(CHR)_n- CH(COOM)(CHR)₀-(CH2)p-(CHR)q-CH3, wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of 0-8, provided that the total number of carbon atoms (including the carboxylate) is in the range of 10 to 18.

In each of the above formulas A, B and C, the species M can be any suitable, especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline earth metal, ammonium, alkanolammonium, di- and tri- alkanolammonium, and C1-C5 alkyl substituted ammonium. Sodium is convenient, as is diethanolammonium.

Preferred secondary soap surfactants for use herein are water- soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l- nonanoic acid, 2-butyl-l-octanoic acid,2-pentyl-l-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, isethionates such as the acyl isethionates, N-acyl taurates,acyl alkyl taurines, fatty acid amides of methyl tauride, alkyl succinates and sulphosuccinates, monoesters of sulphosuccinate (especially saturated and unsaturated Ci2-Cιg monoesters) diesters of sulphosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl C6-20 sarcosinates, sulphates of alky lpolysacchar ides such as the sulfates of Cιo-20 alkylpolyglucoside (the nonionic nonsulfated compounds being described herein). 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, nonionic alkylpolysaccharides and nonionic fatty acid amides.

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. Nonionic 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 Tergitol™ 15-S-9 (the condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol^M 45.9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23- 6.5 (the condensation product of C12-C13 linear alcohol with 6.54 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14- C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45.4 (t e condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), NeodolT 23-3 (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 C13-C15 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 PIuronicTM surfactants, marketed by BASF.

Nonionic EQ condensation products with propylene oxide/ethylene diamine adducts

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

Nonionic 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 1.3 to about 10, preferably from about 1.3 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. The preferred alkylpolyglycosides have the formula

R2θ(C_nH₂nO)t(glycosyl)_x

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose.

Nonionic fatty acid amide surfactant

Fatty acid amide surfactants suitable for use herein are those having the formula:

wherein R9 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each Rio is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and

-(C2H4θ)_xH, where x is in the range of from 1 to 3.

According to the present invention the compositions comprise from 1 % to 20%, preferably from 2% to 15%, most preferably from 3% to 8% of said nonionic surfactants.

Amphoteric surfactant

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

O

I I RC-NHCH2CH2R1

wherein R is a Cg-Cig alkyl group, and Rj is of the general formula:

_/(CH₂)_xC00- _/(CH₂)_xC00-

N or N(+)-CH2CH2θH 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 C14 alkyl group. A preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid. A suitable example of an alkyl aphodicarboxylic acid for use herein in the amphoteric surfactant Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Amine oxide surfactant

According to the present invention in addition to the essential Ci6-i 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: O

wherein Rβ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 6 to 14 carbon atoms, preferably 12 to 14 carbon atoms; and R7 and Rg are independently C1-.3 alkyl or C2-3 hydyroxyalkyl groups, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups. These amine oxide surfactants in particular include C Q- C14 alkyl dimethyl amine oxides and C6-C12 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide and dodecylamidopropyl dimethylamine oxide. Preferred are C 2-C 4 alkyl dimethylamine oxides and mixtures thereof. It has been found that improved cleaning benefits result from the combination of an amine oxide having an average chain length of C 12-14 with an amine oxide having an average chain length of Ci6_ιg.

In addition it has also been found that detergent compositions having improved cleaning can be provided by conventional long chain anionic surfactants such as Ci2-Cιg alkyl carboxylates (secondary soaps), CI I-C15 alkyl benzene sulphates, C12-C14 alkyl sulphates and C12-C14 alkyl ether sulphates containing an average of from 0.5 to 12, preferably 0.5-6 ethylene oxide groups per mole, with the above combination of C12-I4 amine oxide with C16-I8 amine oxide. Particularly preferred are the Ci2-Cι alkyl ethoxyalkyl ethoxy sulphates and mixtures thereof with Cl2-Cig alkyl carboxylates. Such compositions comprise from by weight of the composition from 1 % to 50% preferably from 1 % to 10% of said C 12-14 amine oxide, from 1 % to 15% more preferably from 2% to 10% of said Ci6_ιg amine oxide and from 1 % to 35 more preferably from 5% to 30% of one or more of said anionic surfactants.

Zwitterionic surfactant

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

Betaine 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-Cιg hydrocarbyl group, preferably a C10-C16 alkyl group or Cιo_i6 acylamido alkyl group, each

Rl is typically C1-C3 alkyl, preferably methyl, and R² is a C1-C5 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; C12-I4 acylamidopropylbetaine; Cg. 4 acylamidohexyldiethyl betaine; 4[Ci4-i6 acylmethy lamidodiethylammonio]- 1 -carboxybutane; C 16- 18 acylamidodimethylbetaine; C 12-16 acylamidopentanediethyl-betaine;[Ci2- 16 acylmethylamidodimethylbetaine. Preferred betaines are C12-I8 dimethyl-ammonio hexanoate and the CiO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.

The complex betaines suitable for use herein have the formula:

R - (A)_n [N - (CHRι)_x]_y N - Q (I)

I I

B B

wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, preferably 12 to 14 carbon atoms, A is the group (C(O)), n is 0 or 1, R is hydrogen or a lower alkyl group, x is 2 or 3, y is an integer of 0 to 4, Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium and B is hydrogen or a group Q as defined.

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+R²S03" wherein R is a C -Cι hydrocarbyl group, preferably a C10-C alkyl group, more preferably a C 2-C13 alkyl group, each R is typically C1-C3 alkyl, preferably methyl, and R² is a C1-C 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. Builders

According to the present invention the detergent compositions may comprise builders. Builders are of particular importance in granular detergent compositions. Suitable builders include aluminosilicate having the formula M_z(zAl2 ySiθ2, wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1 ; tis material having a magnesium ion exhange capacity of at least about 50 miligram equivalents of CaCθ3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders which have the formula Na_z[(Alθ2)_z(Siθ2)y]xH2θ, wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264. Commercially available aluminosilicates can be cyrstalline or amorphous in structure and can be naturally or synthetically derived. Preferred synthetic crystalline aluminosilicate ion exhange materials for use herein are available under the designations Zeolite A, Zeolite P (B), Zeolite X, Zeolite Y and Zeolite MAP.

Polymeric Soil Release Agent

According to the present invention the detergent compositions may comprise a polymeric soil release agent. Polymeric soil release agents are characterised by having a hydrophobic and hydrophilic segments.

Polymeric soil relase agents for use herein have a) 1 or more nonioinc hydrophile components consisting of (i) polyoxyethylne segments with a degree of polymerization of at least 2, or (ii) oxypropylen or polyoxypropylne segments with a polymerization degree of 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxyoxypropylene units, or b) 1 or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terethphalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segemtns, or mixtures therein, (iii) poly (vinyl ester segments, preferably poly (vinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents or mixtures thereof, wherein said subsituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof and such celulose derivatives are amphiphilic, whereby they have a sufficent level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically the polyoxyethylene segments of (a)(i) have a degree of polymerization of 2 to 200, preferably 3 to 150, most preferably 6 to 100. Suitable oxy C4-C6 alkylene hydrophobe segments include end caps of polymeric soil release agents such as Mθ3S(CH)_nOCH2CH2θ-, where

M is sodium and n is an integer from 4 to 6.

Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g. C1-C6 vinyl esters, preferably poly9vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. Commercially available materials of this kind include Sokalan marketed by BASF.

Suds suppressor

According to the present invention suds supressors may be incorporated into the detergent compositions herein. Suitable suds suppressors for use herein include high molecular weight hydrocarbons, (such as paraffin, fatty acid estersaliphatic ketones), N-alkylated amino triazines, propylene oxide and monostearyl phosphates.

A preferred suds suppressor for use herein are silicone suds suppressors including polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins and combinations of polyorganosiloxane with silica particles wherein the polyorganosilioxane is chemisorbed of fused onto silica.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of suds controlling agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of from 20cs to about

1500 cs at 25°C

(ii) from about 5 to about 50 parts per 100 parts by weight (i) of siloxane resin composed of (CH3)3 SiOι/2) units of Siθ2 units in the ratio of from

(CH3)3 SiOι/2) units to Siθ2 units of from about 0.6 :1 to 1.2:1 and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.

The silicone suds suppressor for use herein comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene gylcol, all having an average molecular weight of less than about 1000, preferably between about 100 and about 800.

Other suds suppressors for use herein include secondary alcohols (e.g. 2-alykl alkanols) and mixtures thereof with silicone oils. Secondary alcohols include C -16 alkyl alcohols having a Cι_6 chain, preferred is 2- butyl octanol. According to the prsent invention suds suppressors when used for automatic laundry detergents are present in a suds suppressing amount so that the sud formation is controlled. The composition comprises from 0% to 5% of said suds suppressor. Silicone suds suppresors comprise up to about 2%, preferably from 0.001 % to 1 %, most preferably from 0.25% to 05%.

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.

According to the broadest aspect of the present invention the detergent compositions relate to both laundry and dishwashing compositions. Laundry as used herein encompasses granular and heavy duty liquid compositions.

Dishwashing compositions

Another aspect of the present invention relates to dishwashing compositions, in particular automatic and manual dishwashing compositions, especially manual liquid dishwashing compositions. Liquid dishwashing compositions according to the present invention preferably comprise from 0.5% to 30%, more preferably from 1 % to 20% , most preferably from 5% to 15% of the poly hydroxy fatty acid amides and from 1 % to 20%, more preferably from 2% to 15%, most preferably from 3% to 10% of the amine oxide of the present invention having the formula R1R2R3NO wherein R3 is an alkyl group having an average chain length of 16.

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, hydrotopes, calcium and magnesium ions and perfumes and dyes.

In contrast to the manual dishwashing compositions, automatic dishwashing compositions according to the present invention would replace the suds enhancer with a suds suppressor.

Hydrotropes

A hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0% to 10%, preferably from 1 % to 5%, by weight.

Useful hydrotropes include sodium, potassium, and ammonium xylene sulphonates, sodium, potassium, and ammonium toluene sulphonate, sodium, potassium and ammonium cumene sulphonate, and mixtures thereof.

Other compounds useful as hydrotropes herein include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties.

An example of a commercially available alkylpolyethoxy poly carboxylate 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 Cg to Cig 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 Cio to C14 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 Cone, 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 1 to 8 carbon atoms, and n is an integer from 1 to 4. Preferably, R is an alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2. Especially preferred R groups are n-butyl or isobutyl. Preferred solvents of this type are l-n-butoxypropane-2-ol (n = l); and l(2-n-butoxy-l- methylethoxy)propane-2-ol (n=2), and mixtures thereof.

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

Other suitable solvents are benzyl alcohol, and diols such as 2- ethyl- 1,3-hexanediol and 2,2,4-trimethl-l,3-pentanediol.The low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.

The alkane mono and diols, especially the C1-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 addditionally comprise thickening agents, such as polyquaterium cellulose cationic polymer, for example QuatrisoftR available from the Americhol Corporation.

lcum

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 poly hydroxy 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 of from 10:1 to 1:10.

Magnesium

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

If the anionic surfactants are in the acid form, then the magnesium can be added by 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 composition according to the present invention formulated for use in manual dishwashing aplications 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 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.

Examples 1-7

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

C12/13 alkyl 17 9 10 10 - - ethoxy sulphate

C8 alkyl sulphate - - - - 7 2 ave. C16 amine oxide 7 9 3 12 2 1.5 ave. C12/14 alkyl 2 2 1 2 0.5 0.5 amine oxide

C12/14 alkyl di - 1.5 2 - - - methyl betaine

C12 alkyl N-methyl 8 9 10 12 0.5 0.5 glucamide

CIO alkyl 5 5 - 5 - - ethoxylate (ave. 8)

C8 alkyl - - - - 10 - ethoxylate (ave. 6) isopentadecanoic acid - - 10 - - -

C12/14 alkyl - - 5 - - - ethoxy carboxylates

Mg+ + ion 0.5 - 0.3 0.6 - -

Ca+ + ion - 0.3 0.15 0.1 - -

Maleic acid - 0.2 0.3 - - -

Citric acid - - - - - 6

Miranol-R - 2 - - - -

Butyl Carbitol - - - - - 3

Butoxypropylpropanol - - - - - 8

Sodium hydroxide - - - - 0.7 0.6 Polytergent-R - - 2

Lipase - - 0.015-

1 2 3

Amylase - - 0.01

Protease - - 0.05

NeodolR23-3 - -

Minors up to 100%

Examples 7-9

The following formulations represent solid detergent compositions in accordance with the invention.

7 8 9

Zeolite A 25.0 30.0 15.0

Sodium Citrate 5.0 0.0 5.0

Layered silicate SKS6( Na2Siθ5) 0.0 0.0 10.0

Sokolan CP5 (BASF) 4.0 4.0 4.0

Phosphonate DTPMP

(Dequest 2066) 0.4 0.4 0.4

CMC 0.4 0.4 0.4

Perborate Monohydrate 0.0 16.0 0.0

Percarbonate 20.5 0.0 20.0

(13.25% Av02 active)

TAED 5.0 5.0 5.0

Linear alkyl benzene sulphate 0.0 7.0 0.0

C14/15 Alkyl Sulphate 8.0 2.0 10.0

Alkyl Ethoxy Sulphate 2.0 0.2 3.0

C 16/18 alkyl N-methyl glucamide 1.5 2.0 2.0 ave. C16-18 Amine Oxide 1.0 1.0 2.0

C 14/15 Alcohol Ethoxylate(ave.7) 0.0 2.0 0.0

C 12-15 Alcohol Ethoxy late(ave.3) 2.0 0.0 0.0

Sodium carbonate 12.0 15.0 10.0

Silicate amorphous

(2.0 Ratio) 3.0 3.0 0.0

Silicone suppressor 0.4 0.4 0.3

Wax suds suppressor 0.2 0.0 0.2

0.5 0.0 0.0

C18-C20 ^Soaps

Anionic Soil release polymer 1 0.35 0.0 0.0

Optical brightener (Tinopal DMS) 0.15 0.15 0.15

Savinase (4.0 KNPU/g) 1.0 1.0 1.0

Lipolase (100,000Lu/g) 0.4 0.4 0.4

Miscellaneous/Moisture 9.2 10.0 11.0 ¹ A mixture of fully and partially oligomerised esters in which the fully olimerised esters comprise about 50% by weight of the mixture and have the formula:

Claims

1. A detergent composition comprising from 1.0 to 99.9% of a poly hydroxy fatty acid amide, according to the formula

wherein R5 is a C5-C31 hydrocarbyl and R4 is H, a C1-.C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl 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, from 0.1 % to 99% of an amine oxide and optionally other surfactants, characterised in that

said amine oxide is according to the formula R1R2R3N-O, wherein Rl and R2 are independently C1-C3 alkyl or C2-C3 hydroxy alkyl groups and R3 is an alkyl group having on average from 16 to 18 carbon atoms and mixtures thereof.

2. A detergent composition according to Claim 1 comprising from 1% to 60% of the polyhydroxy fatty acid amide and from 0.5% to 20% of said amine oxide.

3. A detergent composition according to either one of claims 1 & 2 comprising from 1.0% to 15% of said amine oxide.

4. A detergent composition according to any one of claims 1-3, wherein

R4 is methyl and R5 is a C9.17 alkyl or alkenyl, Z is - CH2(CHOH)nCHOH, -CH(CH2θH)- (CHOH)n-l-CH2θH, or - CH2-(CHOH)2(CHOR')(CHOH)-CH2θH wherein n is an integer from 3 to 5 inclusive and R' is hydrogen or a cyclic or aliphatic monosaccharide.

5. A detergent composition according to any one of claims 1-4, wherein Z is CH2(CHOH) CH2θH.

6. A detergent composition according to any of the preceding claims, wherein R5 is a Cn_i7 alkyl or alkenyl and Z is a glycityl derived from a reducing sugar or an alkoxylated derivative thereof.

7. A detergent composition according to any of the preceding claims, wherein Z is derived from glucose or maltose or mixtures thereof.

8. A detergent composition according to any of the preceding claims, comprising from 3% to 50% of said poly hydroxy fatty acid amide.

9. A detergent composition according to any of the preceding claims, further comprising an anionic surfactant and/or a nonionic surfactant or mixtures thereof.

10.A physically stable liquid detergent composition according to any of the preceding claims, wherein R3 of said amine oxide is an alkyl group with an average carbon chain length of 16.

11. A physically stable liquid detergent composition according to claim 10, comprising from 1 % to 15% of said amine oxide.

12. A detergent composition according to any of the preceding claims, further comprising from 1 % to 10% by weight of the composition of an amine oxide according to the formula R^R RgNO, wherein R$ and

R7 are independently C1.3 alkyl or C2-3alkyl hydroxy groups and Rs is an alkyl group with an average carbon chain length of Cχ2-Cl4-

13. A detergent composition according to any of the preceding claims, further comprising C12- 4 alkyl betaines.

14. A detergent composition according to any of the preceding claims, further comprising Cn_i6 alkyl carboxylates and/or a C12-I6 alkyl ethoxy carboxylate or mixtures thereof.