AU667047B2 - Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol - Google Patents

Abstract

The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having formula (I), wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, or mixtures thereof, R<2> is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) at least 1 % by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 % by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

Description

OPI DATE 12/01/93 APPLN. ID 22482/92 llllll ,AOJP DATE 11/03/93 PCT NUMBER PCT/US92/04902 'AU9222482 u r It in rrtrtLILA IUN PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 (11) International Publication Number: WO 92/22629 C11D 1/52, 1/72, 1/86 Al C11D 3/02 (43) International Publication Date: 23 December 1992 (23.12.92) (21) International Application Number: (22) International Filing Date: PCT/US92/04902 11 June 1992 (11.06.92) Priority data: 9113139.1 18 June 1991 (18.06.91) (71) Applicant (for all designated States except US): THE PROC- TER GAMBLE COMPANY [US/US]; One Procter Gamble Plaza, Cincinnati, OH 45202 (US).

(72) Inventors; and Inventors/Applicants (for US only) BAILLELY, Gerard, Marcel [FR/GB]; 14 Low Gosforth Court, Newcastle upon Tyne NE3 5QU POWELL, Suzanne [GB/GB]; 8 Longborough Court, Castle Dene, South Gosforth, Newcastle upon Tyne NE3 IYX (GB).

(74)Agent: REED, David; The Procter Gamble Company, Ivorydale Technical Center, 5299 Spring Grove Avenue, Cincinnati, OH 45217-1087 (US).

(81) Designated States: AT (European patent), AU, BB, BE (European patent), BF (OAPI patent), BG, BJ (OAPI patent), BR, CA, CF (OAPI patent), CG (OAPI patent), CH (European patent), CI (OAPI patent), CM (OAPI patent), CS, DE (European patent), DK (European patent), ES (European patent), FI, FR (European patent), GA (OAPI patent), GB (European patent), GN (OAPI patent), GR (European patent), HU, IT (European patent), JP, KP, KR, LK, LU (European patent), MC (European patent), MG, ML (OAPI patent), MN, MR (OA- PI patent), MW, NL (European patent), NO, PL, RO, RU, SD, SE (European patent), SN (OAPI patent), TD (OAPI patent), TG (OAPI patent), US.

Published With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

667047 (54) Title: LAUNDRY DETERGENT CONTAINING A P, LATED ALCOHOL 0 R1 R2- J- N- YHYDROXY FATTY AMIDE AND INSOLUBLE ETHOXY- 7 (I) (57) Abstract The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of at least 1 by weight of the compo- 3ition of a polyhydroxy fatty acid amide having formula wherein R, is H, a C-IC 4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, or mixtures thereof, R 2 is a C 5

-C

31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and at least 1 by weight of the composition of a substantially water-insoluble ethoxylated Cll-C 5 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

WO 92/22629 PCT/I tC920/n9I0 -1- LAUNDRY DETERGENT CONTAINING A POLYHYDROXY FATTY AMIDE AND INSOLUBLE ETHOXYLATED ALCOHOL This Application relates to fabric cleaning compositions and more particularly to fabric cleaning compositions capable of providing grease and oily stain removal.

The surfactant systems of commercially available fabric cleaning compositions are designed to remove a variety of soil types from the fabric surface. The majority of such systems are based on one or more anionic surfactants with minor levels of other surfactant types such as nonionics, ampholytics and cationics. In particular, a combination of a major proportion of anionic and a minor proportion of nonionic surfactant is commonly used to obtain an acceptable balance of particulate soil removal and grease and oily soil removal characteristics. Detergent compositions incorporating surfactant systems in which the major component is nonionic are known in the art, e.g. EP-A-0006268 and GB 2206601 but any commercial application has tended to be of a specialist nature. This is because compositions based on anionic surfactants provide acceptable detergency over a broader spectrum of soil types, display greater compatibility with adjuncts such as optical brighteners and fabric softening additives and are also less aggressive towards fabric dyestuffs and washing machine components.

Accordingly, a need still exists for detergent compositions displaying improved grease and oily soil removal without any sacrifice in the removal of other soil types and without impact on the performance of other detergent ingredients.

WO 92/22629 PCT/US92/04902 -2 The present invention provides laundry detergent compositions which contain nonionic surfactant systems which comprise one or more polyhydroxy fatty acid amides and one or more additional nonionic surfactants. When included in such laundry detergent compositions, these nonionic surfactant systems unexpectedly improve the effectiveness of such compositions against greasy/oily stains across a broad range of laundry conditions.

The commonly assigned copending US Application Serial No.

to 07/578760 tattorney's docket No. 4265) filed 28 September 1990 discloses nonionic surfactant systems comprising combinations of certain polyhydroxy fatty acid amides and one or more additional nonionic surfactants. The polyhydroxy fatty acid amides have the formula R1 R2- -Z wherein RI is H, a C 1

-C

4 hydrocarbyl, 2-hydroxyethyl, 2hydroxypropyl or mixtures thereof, R 2 is a C5-C31 hydrocarbyl and Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof. The weight ratio of the polyhydroxy fatty acid amide to the additional nonionic surfactant can lie in the range from about 1:5 to about 5:1. Other surfactant types such as anionic, cationic, ampholytic, zwitterionic and setaipolar can be included as optional components and detergent compositions incorporating the surfactant systems are also disclosed.

The Applicant has unexpectedly found that detergent compositions incorporating nonionic surfactant systems of this general type comprising certain combinations of pblyhydroxy fatty acid amides and water insoluble ethoxylated nonionic surfactants together with other water soluble surfactants provide unexpected oil and greasy soil removal benefits with no decrease in the detergency performance on other soil types.

(*see page 57A for Equivalent Application) I WO 92/22629 PCT/US92/04902 3 BACKGROUND ART A variety of polyhydroxy fatty acid amides have been described in the art. N-acyl, N-methyl glucamides, for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L.

Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphlphiles," Liquid Crystals, 1988, Volume 3, No. 11, pp 1569-1581, and by A. Muller-Fahrnow, V.

Zabel, M. Steifa, and R. Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J.

Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol.

207, pp 363-366, by J. E. K. Hildreth.

The use of N-alkyl glucanides in detergent compositions has also been discussed. U.S. Patent 2,965,576, issued December 1960 to E. R. Wilson, and G.B. Patent 809.060, published February 18, 1959, assigned to Thomas Hedley Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include -methyl glucamide, added as a low temperature suds enhancing agent. These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.

U.S. Patent 2,703,798, issued March 8, 1955 to A. M.

Schwartz, relates to aqueous detergent compositions containing the condensation reaction product, of N-alkyl glucamine and an aliphatic ester of a fatty acid. The product of this reaction is WO 92/22629 PCT/US92/04902 said to be useable in aqueous detergent compositions without further purification. It is also known to prepare a sulfuric ester of acylated glucamine as disclosed in U.S. Patent 2,717,894, issued September 13, 1955, to A. M. Schwartz.

PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth, relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing of liposomes. Included in this disclosure are compounds of the formula R'CON(R)CH2R" and R"CON(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.

European Patent 0 285 768, published October 12, 1988, H.

Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula RIC(O)N(X)R 2 wherein RI is a C1-C17 (preferably.C7-C17) alkyl, R2 is hydrogen, a CI-C18 (preferably C1-C6) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide. The thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosucclnic acid half aster salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/ N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified. In addition to thickening attributes, the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attributes.

WO 92/22629 PCT/US92/04902 U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylgluca1ide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.

Other glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al., which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxyalkyl-amine of the formula RIC(O)N(R2)CH2(CHOH)nCH20H, wherein RI is a CI-C3 alkyl, R2 is a CIO-C22 alkyl, and n is 3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.

U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxylalkyl compound of the formula RIN(Z)C(O)R 2 wherein RI is a C10-C22 alkyl, R2 is a C7-C21 alkyl, RI and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CHOH)mCH20H where m is 3 or 4.

U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which include compounds of the formula R1N(R)CH(CHOH)nR2 wherein RI is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as RI but both cannot be H, and R2 is CH20H or COOH.

French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of asides of the formula RC(0)N(RI)G wherein R is a carboxylic acid functionality having at least seven carbon atoms, RI is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.

WO 92/22629 PCT/US92/04902, 6 German Patent 1,261,861, February 29, 1968, A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(RI)(R2) wherein R is a sugar residue of glucamine, R1 is a C10-C20 alkyl radical, and R2 is a Ci-C- acyl radical.

G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc. The compounds are expressed by the formula N(R)(RI)C(O)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, R1 is a monovalent hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.

U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker, discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(O)NR 1

(R

2 wherein RC(O) contains from about 10 to about 14 carbon atoms, and RI and R2 each are H or C1-C6 alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.

The use of nonionic surfaetants in detergent compositions is known in the art. U.S. Patent 3,654,166, issued April 4, 1972 to Eckert et al., discloses detergent compositions comprising a surfactant selected fro anionics, zwitterionics and nonionics and an N-alkyl-N-acyl-N-polyhydroxyalkyl compound.

IWO 92/22629 PCT/US92/04902 -7- Another disclosure of the use of nonionic surfactants in detergent compositions is provided by GB Patent 1241754 which teaches that ethylene oxide adducts of C 8

-C

15 substantially unbranched monohydric alcohols having an average ethylene oxide content of from 10% to 51% by weight can serve as detergency improvers for water soluble organic anionic or nonionic surfactants. The improvers are used in a weight ratio of surfactant to improver of from 5:1 to 1:1.

However, the reference does not contemplate the combinations of the present invention that employ water insoluble polyhydroxy fatty acid amide surfactants as well as defined water insoluble ethyoxylated nonionic surfactants.

According to the present invention, there is provided a laundry detergent composition useful for cleaning fabrics in automatic washing machines, said composition comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof, and optionally detergent builder compounds, said composition being characterised in that it comprises, in combination, at least 1% by weight of the composition of a polyhydroxy fatty acid amide having the formula 0

R

1 R2 C N Z where R 1 is H, C 1 -C4 hydrocarbyl, 2-hydroxyethyl, 2hydroxypropyl or a mixture thereof, R2 is C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxy groups directly connected to said chain, or an alkyoxylated derivative thereof; and at least 1% by weight of the composition of a substan:ially water-insoluble ethoxylated C 11

-C

1 5 primary aliphatic alcohol containing an average of no more than five ethylene oxide WO 92/22629 PCT/US92/04902 -8groups per mole and having an ethylene oxide content of less than 50% by weight.

Preferably the composition is granular and comprises from 3 to 15% by weight of anionic surfactant, from 1% to 10% of component and from 1% to 10% of component the weight ratio of anionic surfactant to the combined weights of components and (b) lying in the range from 1:3 to 3:1. More preferably the anionic surfactant comprises a mixture of a major proportion of a water to soluble C14-C15 alkyl sulfate and a minor proportion of a C12-C15 alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate.

The detergent composition of the present invention comprise three essential components, viz. a polyhydroxy fatty acid amide, a water insoluble ethylene oxide adduct of a C11-C15 aliphatic alcohol and a water soluble surfactant that may be anionic, cationic, ampholytic or zwitterionic.

.20 I I I Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended S; to exclude other additives or components or integers.

o 0 WO 92/22629 PCT/US92/04902 -9loolyhvdroxv Fatty Acid Amide The polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula: 0 RI 11 1 RZ N- Z wherein: RI is H, Cj-C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C1 or C2 alkyl, most preferably C1 alkyl methyl); and R 2 is A C 5

-C

31 hydrocarbyl, preferably straight chain c 11

C

19 alkyl or alkanyl, more preferably straight chain c C )9 alkyl or alkanyl, most preferably straight chain C 15

'C

17 alkyl or alkenyl, or mixture thof; and Z is a polyhydioxyhydrocarbyl having a linear hydrocarbyl chain with at least .1 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reactiont; 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 utilized as well as the individual sugars listed above. These corn syrups may yield a six of sugar compoents for Z. It should be understood that it is by no mean* intended to exclude other suitable raw materials. Z preferably will be selected from the 9"~r consisting of -CH 2 .(CHOH)n-CH 2 0H, 1 CH 29 10

"OWN.

1

-CH

2 0oH .CH2-(CHOW),,(CHOR') (COH) -CH2OH, where a is an integer from 3 to S, inclusive, and R' is H or a cyclic or aliphatic monsaccharide, and alkoxylated derivatives thereof.

M~ost preferred are glycityls wherein n is 4, particularly -CXZ. (CC)4-C42WH -In Formutla RI can be, for example, N-methyl, N-ethyl, N-propylt N-isopropyl, N-butyl, K-Z-hydroxy ethyl, or N-2-hydroxy PrOPYL..

WO 92/22629 PCT/US92/04902 10

R

2 -CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula 0 CH3 11 I R2 C N CH2 (CHOH)4CH20H wherein R 2 is a cll-c19 straight-chain alkyl or alkenyl group.

Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglycerlde in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley Co., Ltd., U.S.

Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

In a preferred process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium WO 92/22629 PCT/US92/04902 11 tripolyphosphate, lithium hyd-jxide, sodlum hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about mole to about 50 mole more preferably from about 2.0 mole to about 10 mole on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 138*C to about 170*C for typically from about 20 to about minutes. When triglycerides are utilized in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.

Preferably, this process is carried out as follows: preheating the fatty ester to about 138*C to about 170'C; adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture; mixing the catalyst into the reaction mixture; and stirring for the specified reaction time.

Also preferably, from about 2% to about 20% of preformed linear M-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide produc. is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This seeds the reaction, thereby increasing reaction rate. A detailed experimental procedure is provided below in the Experimental.

The polyhydroxy "fatty acid" amide materials used herein also offer the advantages to the detergent formulator that they can be prepared,wholly or primarily from natural, renewable, non-petro- WO 92/22629 PCT/US92/04902, 12 chemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.

In one particularly preferred embodiment of the invention the polyhydroxy fatty acid amide materials are sourced from tallow fat such that R 2 is a C15-C 1 7 straight chain alkyl group.

It should be recognized that along with the polyhydroxy fatty acid amides of Formula the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.

The level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide-containing compositions added to the detergent contains less than about 10%, preferably less than about of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels of by-products. including such cyclic amide by-product.

The polyhydroxy fatty acid amide component is present at a level of at least 1% by weight of the composition, more preferably at a level of from 1% to 10% by weight and most preferably at a level of from 2% to 6% by weight.

Nonionic Surfactants Laundry detergent compositions of the present invention comprise, in addition to the polyhydroxy fatty acid amide component, one or more of the nonionic surfactants described herein. The nonionic surfactants described herein will hereinafter by referred to as "additional nonionic surfactants." Nonionic compounds other than these additional nonionic surfactants may be optionally included in the nonionic surfactant system of the present invention. These other, optional nonionic compounds will hereinafter be referred to as "optional nonionics." Without intending to be limited thereby, WO 92/22629 PCT/US92/04902 13 it is believed that when such optional nonionics are included in the nonionic surfactant system of the present invention, they do not provide the unexpected stain-removal benefits already described herein.

Additional Nonionic Surfactants Primary C 11

-C

1 5 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol comprise the additional nonionic surfactants useful in compositions of the present invention. Such alcohol ethyoxylates should have an ethylene oxide content of less than by weight and should be water insoluble.

A preferred aliphatic alcohol ethoxylate is a linear or substantially linear aliphatic alcohol containing an average of 12-15 carbon atoms in the alkyl chain, ethoxylated with an average of three ethoxy groups per mole of alcohol.

The additional nonionic surfactant is present at a level of at least preferably from 1% to 10% and more preferably from 1% to 6% by weight of the composition.

The third essential component of laundry detergent compositions in accordance with the invention is one or more water soluble surfactants selected from anionic, cationic, ampholytic and zwitterionic surfactants.

WO 92/22629 WO 2/2629PCr/US92/04902, L4 Anionic Surfactants The laundry detergent compositions of the present invention can contain, in addition to the nonionic surfactant system of the present Invention, one or more anionic surfactants as described below.

Alkyl Ester SUlfgnate Surfactant Alkyl ester sulfonate surfactants hereof include linear Pesters Of C8'.io carboxylic acids fatty &acids) which are sulfonated with gaseous S03 according to "The Journal of the American Oil Chemists Society,* 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, compri so alkyl ester sulfonate suractants of the structural formla: 0

II

wherein R 3 is a Ce-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include mtals such as sodium, potassium, and lithtum, and substituted or unsubstituted ammonium cations, such as monoethanol amine, di ethtnol ami.o, and tri ethanol amine.

Preferably, R 3 is C1O-C16 alkYl, and R 4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R 3 is C10-C16 alkyl.

3oj Alkyl Sulfate Surfactant Alkyl sulfate surfactaints hereof are water soluble salts or acids of the formula ROS03M wherein R preferably is a CIO-C 2 4 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C2o alkyl component, more preferably a C12-ClS alkyl or hydroxyalkyl, and M is H or a cation, aln alkali metal cation sodium, potassium, lithium), or ammonium or substituted ammnoniumn methyl-, dimethyl-t and trimethyl aonium cations and .WO 92/22629 PCT/US92/04902 quaternary ammonium cations such as tetramethyl -ammnonium and dimethyl piperdinium cations and quaternary ammionium cations derived from alkylamines such as ethylamine, di ethyl ani ne, triethylamine, and mixtures thereof, and the like).

Aikyl chains of 12-16 carbon atoms, more preferably 14-15 carbon atoms are preferred.

Alkyl Alkoxylated Sulfate Surfactant Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubstltuted C10-C 24 alkyl or hydroxyalkyl group having a IC2 alkyl component, preferably a C12-C 2 Q alkYl or hydroxyalkyl, more preferably an alkyl group having from 12 to 18 carbon atoms, especially from 12 to 15 carbon atoms.

A is an ethoxy o~r propoxy unit, m is greater than zero, typically between about and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation sodium, potassium, lithium, calcium, magnesium, etc.), ammnonium or substituted-anunonium cation,, Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl -ammnonium cations and qujaternary anmmonium cations such as tetramethyl-ammoniuw and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof. and the like.

Preferred examples of alkyl alkoxylated sulfate surfactants are the

C

12 -Clg alkyl ethoxy sulfates containing an average of up to three ethoxy groups per mole of alkyl ethoxy sulfate.

A particularly preferred surfactant is C 12-C 15 alkyl polyethoxylate sulfate (C12-ClS Other exemplary surfactants, include C 12-C 18 alkyl polyethoxylate sulfate (C 12 -C 18 E(1.AM), C 2-C 18 ailkyl polyethoxylate (2.25) WO 92/22629 WO 9222629PCT/US92/04902, -16 sulfate (Cj 2 -Cj 8 E(2.25)M), C12-Cla alkyl polyethoxylate sulfate (C 12 -C1BE(3.0)M), and C12-C 18 alkyl polyethoxylate (4.C) sulfate (C12-Cj8E(4.0)M), wherein M is conveniently selected from~ sodium and potassium.

otherjjnionic__Surfacant Other anionic surfactants useful for detersive purposes can also be included in the latindry detergent compositions of the present invention. These can include salts (including, for example,, sodium, potassium, ammoonium, and substituted anmmonium salts such as mono-, di- and triethanolamine salts) of soap, Cy-"C2o linear alkylbenzenesulfonates, Ca-C22 primary or secondary al kanesul fonates, C8-C24 ol efi nsul fonates, sul fonated polycarboxylic, acids prepared by sulfonatlon of the pyrolyzed product of alkaline earth metal citrates, as described in British patent specification No. 1,082,179, C8-C24 alkylpolyglycoletherstrlfates (containing, up to. 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffiti sulfonates, alkyl phosphates, isethionates suchl as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated ClZ-C18 monoesters) and diesters of sulfosuctcinates (especially saturated and unsaturated C54Cl2 diesters), acyl sarcosinates, sulfates of alkylpolysacciiar- ZZ ides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary aikyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CI4ZCH2)kCH2COO-H+ wherein R is a CB-C22 alkyl, k is an integer from 0 to 10, and M is a soluble snlt-forming cation. 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 exampl are described in "Surface Active Agents and Detergents' (Vol. I and II by Schwartz, Perry and Berch). A variety of such sorfactants are also generally disclosed in U.S.

Patent 3,929,678, issued December 30, 1975* to Laughlin, et al. at SWO 92/22629 PCT/US92/04902 17 Column 23, 11ne 58 through Colum 29, line 23 (herein incorporated by refertnce).

Preferred anionic surfactant systems employed in the laundry detergent compositions of the invention are free of alkyl benzene sulfonate salts. A highly preferred system comprises a mixture of a major proportion of a water-soluble C14-C15 alkyl sulfate and a minor proportion of a C12-C15 alkyl ethoxysulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. The laundry detergent compositions of the present invention typically comprise lo from about 1% to about 20%, preferably from about 3% to about and most preferably from 5% to 10% by weight of anionic surfactants.

Other Surflctants The laundry detergent coapositions of the present invention may also contain cationic, ampholytic, zwitterionic, and semi-polar surfactants Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants Include the amonium surfactants such as alkyldimethylamonium halogenides, and those surfactants having the formula: [R2(oR 3

[R

4

(R

3 )y]ZR sXwherein RZ is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CHICH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-, -CNzCH2CH2-, and mixtures thereof; each R 4 is selected from the group consisting of CI-C4 alkyl, CI-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups, -CH2COH-CHOICOR6COItCHCZH wherein R 4 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is froa 0 to about 15; and X is any compatible anion..

WO 2/2229 PCT/US92/04902 18 Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

When included therein, the laundry detergent compositions of the present invention, typically comprise from 0% to about preferably from about 3% to about 15% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the- aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about preferably from about 1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in laundry detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin at al., issued December 30, 1975 at column 19, line 38 through Column 22, lina 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

When included therein, the laundry detergent compositions of the'present invention typically comprise from 0% to about preferably from about 1% to about 10% by weight of such zwittarionic surfactants.

WO 92/22629 PCT/US92/04902 19 Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 cirbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

'emi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula 0

R

3

(OR

4 )xN(RS)2 wherein' R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms;

R

4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R groups can be attached to each other, through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include CI0-C18 alkyl dimethyl amine oxides and CB-C12 alkoxy ethyl dihydroxy ethyl amine oxides.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0% to about preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.

WO 92/22629 PCT/US92/04902 20 Builders The laundry detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hardness control.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. Liquid formulations typically comprise at least about more typically from about 5% to about 50%, preferably about 5% to about 30%, by weight of detergent builder. Granular formulations typically comprise at least about more typically from about 10% to about preferably from about 15% to about 50% by weight of th1a detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

Inorganic detergent builders Include, but are not limited to, the alkali metal, ammonium and alkanolamonium salts of polyphosphates (ixemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, and aluminosilicates. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less than about 50°C, especially less than about 4QC. Preferred builder systems are also free of phosphates Exmples of silicate buildors are the alkali metal silicates, particularly those having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:L and layered silicates, such as the layered sodium silicates.

WO 92/22629 PCT/US92/04902 21 Preferred crystalline layered sodium silicates have the general formula NaMSixO2x+ wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A- 3742043, incorporated herein by reference. For the purposes of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the 0- B y and forms of Na2Si2O5. These materials are available from Hoechst AG FRG as respectively NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is 0 -Na2Si205, NaSKS-6.

Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui- WO 92/22629 PCT/US92/04902, 22 carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.

Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: Mz(zAI02-ySi02) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders which have the formula: Naz[(A102)z(Si02)y].xH20 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.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krumuml, et al., issued October 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nal2((A102))2(SiO2)12]'xH20 wherein x is from ?bout 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

WO 92/22629 PC1/US92/04902 23 Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.

Examples of phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-1,1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S.

Patent No. 3,422,021 issued January 14, 1969, to Roy; ind U.S.

Patent Nos. 3,400,148 and 3,422,137 issued September 3, 1968, and January 14, 1969 to Quimby, said disclosures being Incorporated herein by reference.

Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium alkanolammonium) salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972, both of which are incorporated herein by reference.

WO 92/22629 PCT/US92/4902 I 24 A specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:

CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)

wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation. For example, if in the above general formula A and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)-CH2(COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are especially preferred for use herein. Particularly preferred are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97:3 to about 20:80.

These builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference.

Other useful detergency builders include the ether hydroxypolycarboxylates represented by the structure: HO-[C(R)(COOM)-C(R)(COOM)-O]n-H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C1.4 alkyl or Cl- 4 substituted alkyl (preferably R is hydrogen).

Still other ether polycarboxylates include copolymers of maleic anhydride with etnylene or vinyl methyl ether, 1, 3, benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid.

WO 92/2j629 PCT/US92/04902 25 Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid and nitrilotriacetic acid.

Also included are polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Citric builders, citric acid and soluble salts thereof, is a polycarboxylate builder of particular importance for heavy duty liquid eitergent formulations, but can also be used in granular compositions. Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts.

Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.

Also suitable in the laundry deterget compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference.

Useful succinic acid builders include the CS-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkyl succinic acids typically are of the general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., CI1-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, amonium and alkanolammonium salts.

Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenyl- WO 92/22629 PCT/US92/04902 26 succinate (preferred), 2-pentadecenylsuccinate, and the like.

Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-ttracarboxylate, watersoluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester .s then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.

Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, nesaconic acid, fumaric acid, aconitic acid, citraconic acid.and methylenemalonic acid.

Other organic builders known in the art can also be used.

For example, monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of Clo-C20 are typically utilized. The hydrocarbyls can be saturated or unsaturated.

Enzymhes Detersive enzymes can be included in the laundry detergent compositions of the present invention for a variety of reasons WO 92/22629 PCT/US92/04902 27 including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye trinsfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity an/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.

Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name Esperase*. The preparation of this enzyme and analogous enzymes is described in British patent specification No. 1, 2 4 3 ,7a4 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE TM and SAVINASET M by Novo Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc.

(The Netherlands).

Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference. Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence. Protease B is described in European Patent Application Serial No. 87303761.8 filed April 28, 1987, incorporated herein by reference. Methods for prepiration of Protease B are also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985, incorporated herein by reference.

(*see page 57A for Equivalent Application) WO 92/22629 WO 9222629PCr/US92/04902, *28 Amylases include, for example, a-amyiases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Nova), previously incorporated herein by reference. Amylolytic proteins include, for example, RAPIOASETM, International Blo-Synthetics, Inc. and TERMAKYiLTM, Novo Industries.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, incorporated herein by reference* which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2. 247 .832..

Examples of such cellulases are cellulasss produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No. 1,372,034, incorporated herein by reference. Suitable lipases include those which sho%* a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudaoanas fluorescens IAM 1057. This lipase and a method for its 'purification have been described in Japanese Patent Application No. 53-20487t laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,, Japan, under the trade name Lipase P *Amano,u hereinafter referred to as 'Amano-P." Such lipases of the present invention should show a positive iubIological cross reaction with the Amano-P antibody, using the sta~iard and well-known imuunodiffusion procedure according to Ouchtirlony (Act&. Hed. Scan., 133, pages 76-79 (1950)). These WO 92/22629 Df-Clf TQQ1V -29- fA4Y.

lipases, and a method for~ their immuunological cross-reaction with A.xaano-P, are also described in U.S. Patent 4,707,291, Thomn et al., issued November 17, 1987, incorporated herein by reference.

Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERN P 1339 (available under the trade name Amano-8), lipase ex Psueooonas nitroreducens var. lipolyticum FERN P 1338 (available under the trade name Aiwano-CES), lipases ex Chrouobacter VISCOSUM, e.g. Chroaobacter viscasun var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscOsuM lipases from U.S.

Biochemical Corp., U.S.A. and Olsoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. An especially preferred lipase nzyme is manufactured and sold by Novo Industri A/S, Denmark, under the trade name Lipolase (Biotechnology Newswatch, 7 March 1988, page 6) and mentioned, along with other suitable lipases, in EP 0 258 068 (Novo), incorporated herein by reference.

Peroxidase enzymes are used in combination with oxygen source2, percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for 'solution bleaching,* i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.

Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxi dase. Peroxldase-contal n ing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 13, 1989, by 0. Kirk, assigned to Novo Industries A/S. incorporated herein by reference.

A wide range of enzym materials and means for their incorporation into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 te RcCarty at al.

(incorporated herein by reference). Enzymes are further disclosed in U.S. Patent No. 4,101,457, Place at al., issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference. Enzyme -materials useful for liquid detergent formulations, and their incorporat~ion into such formlations, are disclosed in U.S. Patent 4,261,868t Hora et al., issued April 14, 1981, also incorporated herein by reference.

-Enzyms are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 ag, of active anzymo per grin of thet composition.

WO 92/22629 PCr/US92/04902 30 For granular detergents, the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art. In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, preferably formates. See, for example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982, incorporated herein by reference. It has also been proposed to use polyols like glycerol and sorbitol.

Alkoxy-alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al., U. S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al., both incorporated herein by reference, and European Patent Application Publication No. 0 199 405, Application No.

86200586.5, published October 29, 198C, Venegas. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.

Ilelcing Comoounds Bleachino Agents and Bleach Activators The laundry detergent compositions of the present invention ay contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators. When included, present bleaching compounds will typically comprise from about 1% to about 20%, more typically from about 1% to about 10%, of such laundry detergent composition. In general, bleaching compounds are optional components in non-liquid formulations, granular detergents. If present, the amount of bleach activators will WO 92/22629 PFU9140 PCF/US92/04902 31 typically be from about 0.1% to about 60%, more tYPicallY from about 0.5% to about 40% of the bleaching composition.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known.

One category of bleaching agent that can be used eincompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxy.

phthalate hexahydrate, the magnesium salt of meta-chioro perbin~ic acid, 4-nanyluai no-4-oxoperoxybutyrl c acid and diperoxydodecanedloic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartam, issued November 20, 1984, U.S.

Patent Application 74O,446*, Burns et filed June 3, 1985,.

Europian Patent Application 0,133,354, Sanks et aI., published February 20, 1985, and U.S. Patent 4,412,934, Chung et aI., issued November 1, 1983, all of which are incorporated by reference herein. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns, et al., incorporated herein by reference.

The laundry detergent compositions of the present invention will generally include a peroxygen bleaching agent, usually an inorganic perhydrate bleach, normally in the form of the sodium salt.

Suitable perhydrate bleaches may be any of the inorganic salts such as. perborate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal normally sodium, perborate or percarbonate. Sodium perborate can be in the form of the monohydrate of nominal formula NaBO2HiQ2 or the tetrahydrate NaBO2H,)Oi.3H 2 0.

Sodium percarbonate, which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na27CO3.3H 2 0 2 and is available commnercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene, (*see page 57A for Equivalent Application) WO 92/22629 PCr/US92/04902.

-32- 1. 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated into detergent compositions during the manufacturing process. Although the percarbonate can be incorporated into detergent compositions without additional protection, preferred executions of such compositions utilise a coated form of the material. A variety of coatings can be used, but the most economical is sodium silicate of SiO2:Na20 ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to of silicate to solids by weight of the percarbonate. Magnesium silicate can also be included in the coating.

Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution during the washing process) of the peroxy acid corresponding to the bleach activator.

A wide range of bleach activators can be used, examples being disclosed in Spadini et al USP 4179390. Preferred bleach activators include the tetraacetyl alkylene diamines, particularly tetraacetyl ethylene diamine (TAED) and tetraacetyl glycouril (TAGU).

0

I'

R-C-L

wherein R is an alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about carbon atoms and L is a leaving group, the conjugate acid of which has a pKa in the range of from about 4 to about 13. These bleach activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao, at al., incorporated herein by reference, an U.S. Patent 4,412,934, which was previously incorporated herein by reference.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of nonoxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyatniii These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, thi sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. Preferred WO 92/22629 PCT/US92/04902 33 zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al., incorporated herein by reference. Typically, detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.

Polymeric Soil Release Agent Any polymeric soil release agents known to those skilled in the art can be employed in the laundry detergent compositions of the present invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.

This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

Polymeric soil release agents include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.

Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as MethocelR (Dow).

Cellulosic soil release agents also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose. A variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al., incorporated herein by reference.

Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), C1-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide WO 92/22629 PCT/US92/04902 34 backbones. Such materials are known in the art and are described in European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTM HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene 1trephthalate and polyethylene oxide (PEO) terephthalate. Rore specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, which is incorporated by reference.

See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 (incorporated by reference) which discloses similar copolymers.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1. Examples of this polymer include the commercially available material ZelconR 5126 (from Dupont) and MileaseR T (from ICI). These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, which is incorporated herein by reference.

Another preferred polymeric o il release agent is a sulfonated product of a substantially linear ester oligomer comprised of an ollgomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and terminal moieties covalently attached to the backbone, said soil release agent being derived WO 92/22629 PCT/US92/04902 35 from allyl alcohol ethoxylate, dimethylterephthalate, and 1,2 propylene diol, wherein the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups. These soil release agents are described fully in U.S.

Patent 4968451, issued 6 November1990 to J. J. Scheibel and E. P. Gosselink, U.S. Serial No. 07/474,709, filed January 29, 1990, incorporated herein by reference.

Other suitable polymeric soil release agents include the ethyl- or methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., the anionic end-caoped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG), the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH2CH2)n- wherein n is from 12 to about 43 and X is a Ci-C4 alkyl, or preferably methyl, all of these patents being incorporated herein by reference.

Additional soil release polymers include the soil release polymers of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being incorporated herein by reference. The terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, preferably from about 0.1% to about preferably from about 0.2% to about 3.0% by weight of the laundry detergent compositions of the present invention.

Chelating Agents The laundry detergent copositions of the present invention may also optionally contain one or more iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctlonally-substltuted aromatic chelating agents and mixtures thereof, all as hereinafter WO 92/22629 PCT/US92/04902 36 defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure CH2 N (CH2)x COOM, wherein M is hydrog'a, alkali metal, ammonium or substituted ammonium ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the laundry detergent compositions of the present invention when at least low levels of total phosphorus are permitted in detergent compositions. Compounds with one or more, preferably at least two, units of the substructure CH2 N (CH2)x P03M2.

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilotrls (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do I WO 92/22629 PCT/US92/04902 37 not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula

OH

R OH R R

R

wherein at least one R is -S03H or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al., incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g.

mono-or triethanol-amine) salts.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions of the present invention. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Antl-redepositiin Agents Clay soil removal/anti-redaposition agents useful in the laundry detergent compositions of the present invention include polyqthylene glycols and water-soluble ethoxylated amines having clay soil removal and anti-redepositlon properties.

Polyethylene glycol compounds useful in the laundry detergent compositions of the present invention typi:ally have a molecular weight In the range of from about 400 to about 100,000, preferably from about 1,000 to about 20,000, more preferably from about 2,000 to about 12,000, most preferably from about 4,000 to about 8,000.

Such compounds are commercially available and are sold as WO 92/22629 PCT'/US92/04902 38 Carbowaxe, which is available from Union Carbide, located in Danbury, Conn.

The water-soluble ethoxylated amines are preferably selectea from the group consisting of: ethoxylated monoamines having the formula: 2 )2 ethoxylated diamines having the formula: S L L I I X XX or (X-L-)2-N-Rl-N-(R 2 )2 ethoxylated polyamines having the formula: is R 3 4 )tNL-X~p ethoxylated amine polymers having the general formula:

R

2 [(R2)2-N3WERI-NIxERl-N~yERI-N-L-X)z

L

x and mixtures thereof; wherein Al is 0 0 0 0 11 11 11 It P -NCO-, -NCN-, -OCN-, I I f I 1 1 R R R R R R 0 0 0 0 0 11 11 11 11 It -OCO-, -CNC-,

R

or R is H or Cl-C4 alkyl or hydroxyalkyl; R1iIs C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C24C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed; each R2 is CI-C4 or hydroxyalkyl, the moiety -L-Xj or two R 2 together form the moiety -(CH2)rt -AZ-(CH2)s-, wherein A 2 is or -CH2-, r is 1 or 2, s is I or 2, and r s is 3 or 4; X is a nonionic group, an anionic WO 92/22629 PCT/US92/04902 39 group or mixture thereof; R 3 is a substituted C3-C1 2 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites; R 4 is CI-C 1 2 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C 3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or 0-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety 5 0)m(CH2CH20)n]-, wherein R 5 is C 3

-C

4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety -(CH2CH20)n- comprises at least about 50% by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and n is at least about 12; for said diamines, m is from 0 to about 3, and n is at least about 6 when R1 is C 2

-C

3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when RI is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to about 10 and n is at least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x y 4 z is at least 2; and y z is at least 2. The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.

Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference. Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference. Other clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and thi amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985, all of which are incorporated herein by reference.

The most preferred soil release and anti-redeposition agents are ethoxylated tetraethylenepentamine and the polyethylene glycols having a molecular weight in the range of from about 4,000 to about 8,000.

WO 92/22629 PCT/US92/04902 40 Granular detergent compositions which contain such compounds typically contain from about 0.C1% to about 10.0% by weight of the clay removal agent; liquid detergent compositions typically contain from about 0.01% to about 5.0% by weight.

Polymeric Dispersing Agents Polymeric polycarboxylate dispersing agents can advantageously be utilized in the laundry detergent compositions of the present invention. These materials can aid in calcium and magnesium hardness control. In addition to acting as a builder adjunct analogously to the polycarboxylate described above in the Builder description, it is believed, though it is not intended to be limited by theory, that these higher molecular weight dispersing agents can further enhance overall detergent builder performance by inhibiting crystal growth of inorganics, by particulate soil peptization, and by antiredepositions, when used in combination with other builders including lower molecular weight polycarboxylates.

The polycarboxylate materials which can be employed as the polymeric polycarboxylate dispersing agent are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula X

Z

I I C C I I Y COOM n wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; a salt-forming cation and n is from about 30 to about 400.

Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, 2 is hydrogen and H is hydrogen, alkali metal, ammonia or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric WO 92/22629 P~/US92/4902 41 acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid.homopolymers can include, for example, the alkali metal, ammoium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S.

Patent No. 3,308,067, issued March 7, 1967. This patent is incorporated herein by reference.

Acrylic/maleic-based copolymers may also be used as a preferred colponent of the dispersing agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form ranges from about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably from about 7,000 to 60,000.

The ratio of acrylate to maleate segments in s\ch copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/ maleic acid copolymers can include, for example, the alkali metal, aimonium and substituted amonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 1982, which publication is incorporated herein by reference.

WO 92/22629 PCT/US92/04902 42 If utilized, the polymeric dispersing agents will generally comprise from about 0.2% to about 10%, preferably from about 1% to about 5% by weight of the laundry detergent compositions.

Briohtener Optical brighteners or other brightening or whitening agents known to those skilled in the art can be incorporated into the laundry detergent compositions of the present invention. However, the choice of brightener will depend upon a number of factors, such as the type of detergent, the nature of other components present in the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.

The brightener selection is also dependent upon the type of material to be cleaned, cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners which will be effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.

Commercial optical brighteners can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, nethinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.

Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents', M. Zahradnik, Published by John Wiley Sons, New York (1982), the disclosure of which is incorporated herein by reference.

Stilbene derivatives include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacyla-mine derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Certain derivatives of bis(triazinyl)aminostilbene may be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

SWO 92/22629 PCT/US92/04902 43 Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.

Carboxylic acid derivatives include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.

Cinnamic acid derivatives can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.

The styrylazoles can be further subclassified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroups into which styrylazoles may be subclassified.

Other optical brighteners are the derivatives of disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages 737-750 (John Wiley Son, Inc., 1962), the disclosure of which is incorporated herein by reference, and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.

Other optical brighteners ar azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcaegorized into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk-Othmer reference.

Still other optical brighteners are the derivatives of 6-membered-ring heterocycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from-pyrazine and brighteners derived from 4-aminonaphthalamide.

In addition to the brighteners already described, miscellaneous agents may also be useful as brighteners. Examples WO 92/22629 WO 2/2629PCY/US92/04902, 44 of such miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include 1-hydroxy-3,6,8-pyrenetri.

sulfonic acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; phenyllmidazolonedisulfonic acid; and derivatives of pyrazolimequinoline.

Other specific examples of optical brighteners are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988, the disclosure of which is incorporated herein by reference, These brighteners include the PhorwhiteTM series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal available from Ciba-Geigy; Arctic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styrylphenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2is yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the y-amlnocoumarins. Specific' examples of these brighteners include 4-methyl-7-diethylamino coumarin; 1,2-bis(-benzlmidazol-2-yl)ethylene; 1,3-diphenylphrazollnes; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[1,2-d]-oxazole; and 2-(stilbene-4-yl)- 2H-naphthot1,2-d~triazole.

Still other optical brighteners include those disclosed in U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton, the disclosure of which is incorporated herein by reference.

If utilized, the optical brighteners will gerterkuily comprise from about 0.05% to about 2.0%t preferably from about 0.1% to about 1.0% by weight of the laundry detergent compositions.- Suds Suppressors Compounds known, or which become known, for reducing or suppressing the formation of suds can be incorpirated into the laundry detergent compositions of the present invention. The incorpo~ration of such materials, hereinafter 'suds suppressors," can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositions include a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide WO 92/22629 PCT/US92/04902 45 surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading automatic washing machines. These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consequently, in reduced cleaning performance. The use of suds suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.

A wide variety of materials may be used as suds suppressors.

Suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S.

Patent 2,954,347, issued September 27, 1960 to Wayne St. John, said patent being incorporated herein by reference. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. These materials are a preferred category of suds suppressor for detergent compositions.

The laundry detergent compositions of the present invention may also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g.

stearone), etc. Other suds inhibitors include N-alkylated amino trizlines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and WO 92/22629 PCT/US92/04902 46 monostearyl di-alkall metal sodium, potassium, lithium) phosphates and phosphate esters. The hydrocarbons, such as paraffin and haloparaffin, can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40"C and about 5"C, and a minimum boiling point not less than about 11OC (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 1004C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al., incorporated herein by reference. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used.. in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.

Silicone suds suppressors ars well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. and European Patent Application. No. 89307851.9, published February 7, 1990, by Starch, M. both incorporated herein by reference.

Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granclar detergent I WO 9222629 PCT/US92/04902 47 compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 es. at (ii) from about 5 to about 50 parts per 100 parts by weight of of siloxane resin composed of (CH3)3 Si01/2 units of Si02 units in a ratio of from (CH3)3 Si01/ 2 units and to Si02 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of of a solid silica gel; Suds suppressors, when utilized, are present in a "suds suppressing amount." By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will control the suds to the extent desired. The amount of suds control will vary with the detergent surfactant selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desired suds control than with low foaming surfactants.

The laundry detergent compositions of the present invention will generally comprise from 0% to about 5% of suds suppressor.

When utilized as suds suppressors, monocarboxylic fatty acids, and salts. thereof, will be present typically in amounts up to about by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness. of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of WO 92/22629 PCT/US92/04902 48 silicone suds suppressor is used, more preferably from about 0.25% to about As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphates are generally utilized in amounts ranging from about 0.1% to about 2% by weight of the compositions.

Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about although higher levels can be used.

Other Inaredients A wide variety of other ingredients which can be included in the laundry detergent compositions of the present invention include other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from about 2 to about 6 carbon atoms and from about 2 to about 6 hydroxy groups propylene glycol, ethylene glycol, glycerine, and 1,3-propanediol) can also be used.

The laundry detergent compositions of the present invention will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art.

This invention further provides a method for cleaning substrates, such as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate with a detergent composition containing WO 92/22629 1T/ US92/04902 49 the nonionic surfactant system of the present invention, wherein the weight ratio of polyhydroxy fatty acid amide to additional surfactant in the nonionic surfactant system is in the range of from about 1:5 to about 5:1, in the presence of a solvent such as water or a water-misciblK solvent primary and secondary alcohols). Agitation is preferably provided for enhancing cleaning. Suitable means for providing agitation include rubbing by hand preferably with the aid of a brush, or other cleaning device, automatic laundry washing machines, automatic dishwashers, etc.

EXPEERIMENTAL

This exemplifies a process for making a N-methyl, 1-deoxyglucityl lauramide surfactant fr use herein. Although a skilled chemist can vary apparatus configuration, one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium. The other two necks of the flask are fitted with a nitrogen sweep and a wide-bore sidearm (caution: a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet. The latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap. A 500 watt heating mantle with a variable transformer temperature controller ("Variac') used to heat the reaction is so placed on a lab-Jack that it may be readily raised or lowered to further control temperature of the reaction.

N-methylglucamine (195 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter Gamble CE 1270, 220.9 1.0 mole) are placed in a flask. The solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately minutes). When the melt temperature reaches 145' C, catalyst (anhydrous powdered sodium carbonate, 10.5 0.1 mole, J. T.

Baker) is added. The nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 5 inches (5/31 atm.) Hg.

vacuum. From this point on, the reaction temperature is held at WO 92/22629) I'Cr/US92/04902 50 150* C by adjusting the Variac and/or by raising or lowering the mantle.

Within 7 minutes, first methanol bubbles are sighted at the meniscus of the reaction mixture. A vigorous reaction soon follows. Methanol is distilled over until its rate subsides. The vacuum is adjusted to give about 10 inches Hg. (10/31 atm.) vacuum. The vacuum is increased approximately as follows (in inches Hg. at minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of methanol evolution, heating and stirring are discontinued co-incident with some foaming. The product is cooled and solidifies.

The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.

The invention is illustrated in the following examples in which all amounts are by weight unless otherwise specified.

.WO 92/22629 PCT/US92/04902 51 In the Examples, the abbreviated component identifications have the following meanings: C12LAS

TGA

TAS

C14/15AS C12/15AE3S TAEn 45E7 25E3 Sodium linear C 12 alkyl benzene sulfonate Glucityl tallow fatty acid amide Sodium tallow alcohol sulfate Sodium C14-C15 alkyl, sulfate Sodium C12-C15 alkyl ether sulfate containing an average of three moles of ethylene oxide per mole of alkyl sulfate Tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol.

A C14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide.

S A C12-C15 primary alcohol condensed with an average of 3 moles of ethylene oxide.

S Tetraacetyl ethylene diamine Amorphous Sodium Silicate (SiO2:Na20 ratio normally follows).

Anhydrous sodium carbonate Sodium carboxymethyl cellulose S Hydrated Sodium Aluminosilicate of formula Nal2(A102SiO2)12.27H20 having a primary particle size in the range from 1 to 10 micrometers Tri-sodium citrate dihydrate Copolymer of 1:4 maleic anhydride/acrylic acid, average molecular weight about 80,000.

TAED

Silicate Carbonate

CMC

Zeolite A Citrate

MA/AA

WO 92/22629 WO 92/2629 C/US92/04902, 52 Perborate Monohydrate Enzyme Brightener:

DETPMP

Anhydrous sodium perborate bleach empirical formula NaB02.H 2 0 2 Mixed proteolytic and amyloytic enzyme sold by Novo Industries AS.

Disodium. 4,4'-bis(2-morpholino-4anilino-s-triazin-6-ylamino)stilbene- 2:2'-disulphonate.

Diethylene triamine penta (Methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 25 paraffin wax Mpt 50 17 hydrophobic silica, 58 paraffin oil.

SUDS

Suppressor I WO 2/22629 PCr/US92/04902 53 Example I The following particulate detergent compositions were prepared: A B C TAS 2.43

C

1 4/ 1 5AS 5.4

C

12 /15AE 3 S TGA 3.5 25E3 3.0 Zeolite A 15.0 Citrate Silicate (2.0 ratio) Carbonate 13.6 MA/AA 4.25 DETPMP 0.38 CMC 0.48 TAED Perborate 16.0 Enzyme 1.4 Brightener 0.19 Suds Suppressor The Performance of the three compositions was compared in both Tergotometer Tests and in full scale washing machine tests.

Tergotometer Tests 6 x 2 litre metal pots were filled with water of 120 Clark Hardness (Ca:Mg 4:1) and heated to 60°C. 14g of product was added to each pot and dissolved/dispersed to give a product weight concentration of Stained 7.5 cm x 7.5 cm cotton and polycotton fabric swatches were made by applying separate stripes of artificial sebum, shoe polish and dirty motor oil (DMO) uniformly on to each fabric swatch. A swatch of each fabric type was then attached to the paddle of each pot and the paddles were then agitated in the pots for 45 minutes. The total number of replicates for each product was 6, The swatches were then rinsed in cold water, dried overnight and then assessed by an expert panel using a five point Scheff6 scale.

WO 92/22629 PCT/US92/04902 54 Washing Machine Tests AEG Lavamat 980 automatic washing machines were used to carry out a similar comparison of the products. A 45 minute main wash cycle at 60*C was selected and a product concentration of 0.7% in 12° Clark Hardness water (Ca:Mg 4:1) was used. Six replicates for each product were carried out. Each wash load comprised 3kg of realistically soiled ballast fabrics composed of cotton sheets and towels together with polycotton items to give a cotton:polycotton weight ratio of approximately 3:1, together with sets of stained swatches.

The stain sets comprised: 2 greasy stains on cotton (lipstick, DMO).

2 greasy stains on polyester (make up, polish).

After rinsing with cold water, each swatch was dried and then assessed by an expert panel using a five point Scheffd scale.

The results of both test techniques are set out below.

The LH column shows the advantage for Composition A over Composition B while the RH column shows the advantage for Composition A over Composition C.

WO 92/22629 IPCT/US92/04902 55 Tergotometer A/B A/C Cotton sebum -0.3 -0.3 polish +0.6 +0.2 -DMO +0.8 Polycotton sebum +0.2 +0.4 polish +0.8 to DMO Washing Machine Lipstick/Cotton +0.2 DMO/cotton Makeup/polyester +1.0 +0.3 Polish/polyester +1.l(s) statistically significant at 95 confidence level.

Product C represents a prior art composition and the comparison A/C shows that composition A, in accordance with the invention,provides stain removal benefits relative to Composition C over a wide spectrum of soil types and fabrics. The comparison of compositions A&B shows the surprising benefit provided by the use of a combination in accordance with the invention relative to that provided by use of a higher level of the polyhydroxy fatty acid amide alone.

WO 92/22629 PCT/US92/04902 56 Example II Composition A of Example I was compared to a commercially available detergent composition which differed from Composition A only in that the 45AS, 25AE3S, TGA and 25E3 components were replaced by 7.6% C12 LAS, 3% 45E7 and 1.1%

TAE

11 The comparison was carried out in AEG Lavamat 980 washing machines using the wash conditions and procedure of Example 1 and a variety of stains on cotton, polycotton and polyester fabric swatches. Assessment of the washed fabric swatches by an o1 expert panel using a five point Scheff6 scale showed that Composition A provided a stain removal benefit over Composition D of 2 psu on polish froim polyester 1 psu on DMO from polycotton 1.5 psu on make up from cotton jWO 92/22629 PCT/US92/04902 57 Example III The performance of Composition A of Example I was compared to that of two further detergent Compositions D and E which differed from A only in that the 25E3 component was replaced by 68E3 and 68E5 respectively, where 68E3 and 68E5 are C 16

-C

18 predominantly linear primary alcohols condensed with an average of three and five moles of ethylene oxide respectively. The performance comparisons were lade using the conditions and procedure of the tergotometer test of Example I.

Assessment of the washed fabric swatches by an expert panel using a five point Scheff6scale showed that Composition A, in accordance with the invention, provided significant stain removal benefits over both compositions D and E, neither of which is a composition in accord with the invention.

The results of the comparisons are set out below.

The LH column shows the advantage for Composition A over Composition D while the RH column shows the advantage for Composition A over Composition E.

A/D A/E Polycotton Sebum +0.8s +0.3 polish -0.3 -0.6 DMO +1.8s Polyester sebum +2.6s +2.7s polish +1.6s DMO +0.8s s= statistically significant at 95% confidence level WO 92/22629 PCr/US92/ 04902 (*Equivalent Applications:) USSN 07/578,760 -,PCT/11S91/06980 published as W092/06160 European Application lit). 87303761.8 =European Patent 0,251,446, published 7 January 1988 USSN 740,446 European Patent 0,170,386

Claims (4)

1. 2-hydroxypropyl or a mixture thereof, R2 is C 5 -C 31 hydrocarbyl and Z is a poly hydroxyhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxy groups directly connected to said chain, or an alkyoxylated derivative thereof; and at least 1% by weight of the composition of a substantially water-insoluble ethoxylated Cl1-C 1 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than by weight. WO 92/22629 PCT/US92/04902 59 2) A laundry detergent composition according to claim 1 wherein component a) is a polyhydroxy fatty acid amide of formula 0 R1 I 1 R2- C -N -CH2(CHOH) 4 wherein R2 is a C11-C 19 straight chain alkyl or alkenyl group. 3) A laundry detergent composition according to either one of claims 1 or 2 wherein R 2 is a C15-C 19 straight chain alkyl or alkenyl group or a mixture thereof and R 1 is methyl. 4) A laundry detergent composition according to any one of claims 1-3 wherein R 2 is a C15-C17 straight chain alkyl group derived from tallow fat. A laundry detergent composition according to any one of claims 1-4 wherein component b) comprises a linear or substantially linear aliphatic alcohol containing an average of 12-15 carbon atoms in the alkyl chain ethoxylated with an average of three ethoxy groups per mole of alcohol. 6) A granular laundry detergent composition according to any one of claims 1-5 comprising from 3% to 15% by weight of anionic surfactant, from 1% to 10% of component and from 1% to 10% of component the ratio of the weight of anionic surfactant to the combined weights of components a) and b) lying in the range from 1:3 to 3:1. S I I WO 92/22629 PfCT/US92/04902 60 7) A granular laundry detergent composition according to claim 6 wherein the anionic surfactant comprises water- soluble C 1 2-C 1 8 alkyl sulfates, C 1 2-C 18 alkyl ethoxy sulfates containing an average of up to three ethoxy groups per mole of alkyl ethoxy sulfate and mixtures thereof. 8) A granular laundry detergent composition according to claim 7 wherein the anionic surfactant is free of alkyl benzene sulfonate salts. 9) A granular laundry detergent composition according to any one of claims 6-8 wherein the anionic surfactant comprises a mixture-of a major proportion, by weight of the mixture, of a water soluble C 1
2. 4-C 1 5 alkyl sulfate and a minor proportion, by weight of the mixture, of a C 1 2- C 1 S alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. A granular laundry detergent composition according to any one of claims 6-9 incorporating a non phosphate detergent builder system. 11) A granular laundry detergent composition according to claim 10 wherein the detergent builder is selected from synthetic crystalline or amorphous zeolite aluminosilicates, alkali metal carbonates, bicarbonates and organic polycarboxylates, alkali metal silicates, crystalline layered sodium silicates, water-soluble salts of acrylic acid homopolymers or acrylic acid copolymers with maleic anhydride, amino polycarboxylates and mixtures of any of the foregoing.
3. 12. A laundry detergent composition according to claim 1 substantially as herein described with reference to any one of the Examples. DATED: 11 September, 1995 THE PROCTER GAMBLE COMPANY By their Patent Attorneys PHILLIPS ORMONDE FITZPATRICK INTERATIONAL SEARCH REPORT International applicati4n No. PCT(US92/04902 A. CLASSIFICATION OF SUBJECT MATTER :C11D, 1/S2,1172,1/86,3/02 US CL :252/174.21,529,531 ,5'2,540,548,550,551 ,559 According to International Patent Clussiflcation (IPC) ar to both national class ificition and IPC Minimum documentation searched (classification system followed by classification- symbols) Documentation searched other than minimum documentation to the extent that such documents are included in the fields search :d Electronic data basc consulted during the international search (name of data basr, and, where practicable, search terms used) none C. DOCUMvENTS CONSIDN.RED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant palsages Rdlevant to claim No. Y US,A, 2,965,576, (Wilson), 20 December 1960, Sec column 2 and'the example. 1-4 Y US,A, 3,654,166, (Eckert), 04 April 1972. See column 5, lines 1-36 and column 5, lines 1-4
4. 36-41 and 53-60. Y USA, 3,868,336, (Mazzla), 25 February 1975, Ste column 6, lines 57-65 and tables IV- 1-4 VuI. Y US.A, 3,925,224, (Winston), 0 December 1975. Sec col, 7, lines 60-65 and claims 1 and 1-4 7. Y US,A, 4,072,621, (Rose), 07 February 1978. See claim 1. 1-4 Y US,A, 4,110,262 (ArnAu), 29 August 1978. Sec examples I-IV, IX And X in coiumti 16. 1-4 Further documents are listed In the continuatin of Box C, ElSec patent famrilly annex, specit categotes of cited docuamaxb lT auc do mmlpithUhed dt the IrsenAtioial Miig dIata or pflority dame sad mo" in conflict with th* spplication 4u cited to tindersiand the dooctnw eodfinin the Seneral state of the ant whic ia bo coouidenrd prncpi or theor uderving the invnt to ea in doinep*Usha 00eem Wtatttec~toa domtant of peziktkt relevance; the ZLae Invention cannot be V eaikrdo~nt ubU onor ftertheintmilondfilal atecoosidered novel or musot be couildered to itivolve an inventive step VL dommennt wh"c may tbww dotst 0o price"t clalto(s) or which 6 wb "h documaA~ is taken alone cited to estbli~h the publicatiots data of snothet citatiou or' We 'Y dcm of peiua Ivne h l~Inetocao e doctat reterra to an orA disclosure, we, extubitioo ot odthe combined with one or more ade shdocme sch covabirazion memo bein b"t eaA itsedtheart doczmentpulsed ptior to the International rfilin date biA Wer ta doctA nent meber or the same patent famiy' the priority date Date of the actual completion of the International search Date of mailing of the international search report 17 SEPTEMBER 1992 22 DOCT1992 .A Name and mnalling address of the ISM) Authorized officer Comotiauioner of 1patents and Trademnarks Box P'c'r DENNIS L. ALBRECHT Washington, D.C. 20231 Facsimile No. NOT APPLICABLE ITelephone No. (703) 308-2525 Form PCTIISAI210 (second shect)(iuly 1992)*