IE921961A1 - Detergent compositions - 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

DETERGENT COMPOSITIONS 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. - 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. 07/578760 (attorney'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 Ri o • - ll R2-C-N-Z wherein Rj is H, a C1-C4 hydrocarbyl, 2-hydroxyethyl, 2hydroxypropyl or mixtures thereof, R^ 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 scmipolar 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 polyhydroxy 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.

BACKGROUND ART A variety of polyhydroxy fatty acid amides have been described 1n the art. N-acyl, N-methyl glucamldes, for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn 1n ’The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amph1ph11es, Liquid Crystals, 1988, Volume 3, No. 11, pp 1589-1581, and by A. Muller-Fahrnow, V.

Zabel, M. Steifa, and R. Hilgenfeld In Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamlde, J. Chem. Soc. Chem. Commun., 1988, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial Interest recently for use 1n biochemistry, for example 1n the dissociation of biological membranes. See, for example, the journal article N-D-G1uco-N-methy1-a1kinam1de Compounds, a New Class of Non-Ion1c Detergents For Membrane Biochemistry, Biochem. J. (1982), Vol. 207, pp 363-366, by J. Ε. K. Hildreth.

The-use of N-alkyl glucamldes 1n detergent compositions has also been discussed. U.S. Patent 2,965,576, Issued December 20, 1960 to E. R. Wilson, and 6.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley 8 Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can Include N-methyl glucamlde, 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 1s also generally Indicated that additional constituents to Impart desirable properties to the composition can also be Included 1n the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.

U.S. Patent 2,703,798, Issued March 8, 195S to A. M. Schwartz, relates to aqueous detergent compositions containing the condensation reaction product, of N-alkyl glucamlne and an aliphatic ester of a fatty acid. Tho product of this reaction 1s 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 1n U.S. Patent 2,717,894, issued September 13, 1955, to A. H. Schwartz.

PCT International Application WO 83/04412, published Oecember 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 1n cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and 1n 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 RCON(R)R' wherein R 1s hydrogen or an organic grouping, R* ts an aliphatic hydrocarbon IS group of at least three carbon atoms, and R 1s 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 1n aqueous detergent systems. Included are amides of the formula RlC(0)N(X)R2 wherein Rl 1s a C1-C17 (preferably.C7-C17) alkyl, R2 1s hydrogen, a Ci-Cjg (preferably C1-C5) alkyl» or an alkylene oxide, and X Is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamldo. Tho 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, sucb as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkyl phenol polyglycol other, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/ N-methyl coconut fatty acid glucamlde/nonlonlc 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.

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-alkylglucamide nonionic surfactant which 1s selected from N-methyl,N-sorb1tyl lauramide and N-methyl, N-sorb1tyl myristamlde.

Other glucamlde surfactants are disclosed, for example, 1n OT 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 RlC(O)N(R2)CH2(CHOH)nCH2OH, wherein Ri 1s a C1-C3 alkyl, «2 is « Cl0*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 Η. H. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zw1tter1on1c, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxyl alkyl compound of the formula RiN(Z)C(0)R2 wherein Rj 1s a Ci0c22 alkyl, ^2 1* * c7‘c21 alkyl, Rj and R2 total from 23 to 39 carbon atoms, and Z 1s a polyhydroxy alkyl which can be -CH2(CHOH)„CH2OH where m 1s 3 or 4.

U.S. Patent 4,021,539, Issued May 3, 1977, to H. Mflller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which Include compounds of the formula RlN(R)CH(CH0H)aR2 wherein Rl Is H, lower alkyl, hydroxy-lower alkyl» or aminoalkyl, as well as heterocyclic aminoalkyl, R Is the seme as Ri but both cannot be H, and Rj Is CH2OH or COOH.

French Patent 1,360,018, April 28, 1963, assigned to CooMrclal Solvents Corporation, relates to solutions of formldehyde stabilized against polymerization with the addition of amides of the formula RC(O)N(Ri)G wherein R 1s a carboxylic acid functionality having at least seven carbon atoms, Ri 1s hydrogen or a lower alkyl group, and 6 Is a glycltol radical with at least 5 carbon atoms.

German Patent 1,261,861, February 29, 1968, A. Heins, relates to glucamlne derivatives useful as wetting and dispersing agents of the formula N(R)(Rj)(R2) wherein R 1s a sugar residue of glucamlne, Ri 1s a C1Q-C20 alkyl radical, and R2 1s a C1-C5 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 M(R,(Ri)C(O)R2 wherein R Is the residue of an anhydrlzed hexane pentol or a carboxylic acid ester thereof, Ri 1s 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 0. T. Hooker, discloses solid tolTet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a non1on1c surfactant selected from certain propylene oxide-ethylenedlamine-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(0)NRl(R2) wherein RC(O, contains from about 10 to about 14 carbon atoms, and Ri and R2 each are H or Ci-Cg 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 1s found 1n U.S. Patent 3,312,626, also Issued April 4, 1967 to 0. T. Hooker.

The use of nonionic surfactants in detergent compositions is known 1n the art. U.S. Patent 3,654,166, Issued April 4, 1972 to Eckert et al., discloses detergent compositions comprising a surfactant selected from anionics, zwltterlonlcs and nonionics and an N-alkyl-N-acyl-M-polyhydroxyalkyl compound. - 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 Cg-Ci5 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, (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having the formula O Ri II I R2- C -N -Z where Ri is H, C1-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 (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.

Preferably the composition is granular and comprises from 3 % to 15% by weight of anionic surfactant, from 1% to 10% of component (a) and from 1% to 10% of component (b), the weight ratio of anionic surfactant to the combined weights of components (a) 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 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.

I - 9 Polvhvdrovv Fattv Acid Amid· Th* polyhydroxy fatty acid amide surfactant component of the present Invention comprise» compounds of the structural formula: Rl II I (I) ni - C - N - I wherein: Rl Is H, Ci*C< hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (I.e., methyl); and R2 Is a C5-C31 hydrocarbyl, preferably straight chain cifCl9 alkyl or alkenyl, more preferably straight chain c{5-c]9 alkyl or alkenyl, most preferably straight chain C15-C47 alkyl or alkenyl, or mixture thereof; and Z 1s a polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or am alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be. derived fro· a reducing sugar In a reductive amination reaction; eore preferably Z is a glycltyl. Suitable reducing sugars Include glucose, fructose, maltose, laetose, galactose, mannose, and xylose. As ram materials, high dextrose com syrup, high fructose com syrup, and high maltose com syrup can be utilised as well as the Individual sugars listed above. These 2S com syrups may yield e mix of sugar components for Z. It should be understood that 1t 1s by ne eoans Intended to exclude other suitable ra» eatarlals. Z preferably will be selected fro· the groups consisting of n-CHtOH, -CH(QftQH)-(CHOH)n.t-CH|OH, -€Mt-(CH0H)2(a«»')(CMH)-CH2OH, where 0 Is am Integer fro· 3 to 9, inclusive, and A* Is H or 9 cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred am glycltyls wherein n Is 4, particularly -CHj-(CH0H,4-CH20H.

-In Formula (I), Rl cam be, for example, N-mthyl, M-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or Μ-2-hydroxy propyl.

R*-C0-N< can be, for example, cocamide, stearamide, oleamide, lauramlde, myrlstamlde, capricaralde, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfruct1tyl, l-deoxymalt1tyl, 5 l-deoxylact1ty1, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotrlotltyl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula CH3 II I R2 - C - N - CH2 - (CH0H)u-c19 straight-chain alkyl or alkenyl group.

Methods for making polyhydroxy fatty acid amides are known 1n 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 triglyceride 1n 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 6.B. Patent Specification 809,060, published February 18, 1959, by Thornes 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 N. Schwertz, 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-hyd^oxyalkyl, N-deoxyglyc1tyl fatty acid amides wherein the glycltyl component 1s derived from glucose and the N-alkyl or N-hydroxyalkyl functionality Is N-methyl, N-athyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product 1s made by reacting N-alkyl- or N-hydroxyalkyl -glucamlne with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides 1n the presence of a catalyst selected from the group consisting of trlllthlimi phosphate, trisodium phosphate, tripotassium phosphate, tetresodlum pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, d1sodium tartrate, di potassium 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 1s preferably from about 0.5 mole X to about 50 mole X, more preferably from about 2.0 mole X to about 10 mole X, on an N-alkyl or N-hydroxyalkyl -glucamlne molar basis. The reaction 1s preferably carried out at from about 138*C to about 170*C for typically from about 20 to about 90 minutes. When triglycerides are utilized 1n the reaction mixture as the fatty ester source, the reaction 1s also preferably carried out using from about 1 to about 10 weight X of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected fro*'saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamldm surfactant, and mixtures thereof.

Preferably, this process 1s carried out as follows: (a) preheating the fatty estor to about 138’C to about 170*0; (b) adding the N-alkyl or N-hydroxyal kyl glucamlne to the heated fatty acid ester and mixing to the extent needed to form a two-phase llquid/llguld mixture; (c) mixing the catalyst Into th· reaction mixture; and (d) stirring for th· specified reaction time.

Also preferably, from about 2X to about 20X of preformed linear K-alkyl/N-hydroxyalkyl, N-l 1 near glucosyl fatty acid amide product le 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 1s 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 fro* natural, renewable, non-petro35 - 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 R2 is a C15-C17 straight chain alkyl group.

It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), 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 4%, 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, - 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 C11-C15 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 50% 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 1%, 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. - 14 Anionic Surfactant* The laundry detergent composition» 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.

Alkvl Ester Sulfonate Surfactant Alkyl ester sulfonate surfactants hereof include linear esters of Cg-C2O carboxylic acids (1.e., fatty acids) which are sulfonated with gaseous SO3 according to The Journal of the American 011 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, comprise alkyl ester sulfonate surfactants of the structural formula: R3 - CH - C - OR* I SO3H wherein Rl Is a C&-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R* 1s a Cj-Cg 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 metals such as sodium, potassium, and llthtum, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R^ Is Cig-Cie alkyl, and R* Is methyl, ethyl or Isopropyl. Especially preferred are the methyl ester sulfonates wherein R* Is Cio*Ci6 alkyl.

Alkyl Sulfate Surfactant Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3N wherein R preferably is a Cio-C2< hydrocarbyl, preferably an alkyl or hydroxyelkyl having a C10-C20 alkyl component, more preferably a Ci2'c18 alkyl or hydroxyalkyl, and N 1s H or a cation, e.g., aft alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl plperdlnlum cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).

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

Alkvi Alkoxylated Sulfate Surfactant Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A)BS03M wherein R is an unsubstituted Cio-C2< alkyl or hydroxyalkyl group having a Cio-C24 alkyl component, preferaMy a C12-C20 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 or propoxy unit, m 1s greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and H Is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substltuted-ammonlum cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations Include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl plperdlnlum cations and those derived from alkylamines such as ethylamine, diethylamine, tr1 ethyl ami ne,_ mixtures thereof, and the like.

Preferred examples of alkyl alkoxylated sulfate surfactants are the Cl2-Cl8 ethoxy sulfites containing an average of up to three ethoxy groups per mole of alkyl ethoxy sulfate.

A particularly preferred surfactant is C 12*^15 alkyl polyethoxylate (3.0) sulfate (C12-C15 E(3.0)M). Other exemplary surfactants include C 12-^18 polyethoxylate ¢1.0) sulfate (C12-C18 E(l.O)M), C12-C18 alkyl polyethoxylate (2.25) sulfate (Ci2-Ci8£(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate (Ci2-Ci8E(3.0)M), and C12-C18 alkyl polyethoxylate (4.0) sulfate (Ci2-Ci8E(4»0)M), wherein M 1s conveniently selected from sodium and potassium.

Other Anionic Surfactants Other anionic surfactants useful for detersive purposes can also be Included 1n the laundry detergent compositions of the present Invention. These can Include salts (Including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkanesulfonates, C8-C24 olefInsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described 1n British patent specification No. 1,082,179, C8-C24 alkylpolyglycolethersulfates (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, paraffin sulfonates, alkyl phosphates, Isethionates such as the acyl Isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosucd nates (especially saturated and unsaturated Cj2*Cl8 monoesters) and diesters of sulfosucdnates (especially saturated and unsaturated C5-C12 diesters), acyl sarcoslnates, sulfates of alkylpolysacchar25 ides such as th· sulfates of alkylpelyglucoslde (tho nonionic nonsulfated compounds be’lng described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)|(CH2COO’tt* wherein R Is a Cg-C22 alkyl, k 1s an Integer from 0 to 10» and N Is a solublo salt-forming cation. Rosin adds and hydrogenated rosin adds are also suitable, such as rosin, hydrogenated rosin, and rosin adds and hydrogenated rosin acids present 1n or derived from tall oil. Further examples are described 1n Surface Active Agents and Detergents (Vol. I and II by Schwartz, Perry and Borch). A variety of such surfactants are also generally disclosed 1n U.S. Patent 3,929,678, Issued December 30, 1975 to Laughlin, et al. at «Ε 921961 'i7 ' Colen », ltn· SS throu«h CaluM 2,, llrra a (h.r«,i, Incorporated by reference).

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 from about 1% to about 20%, preferably from about 3% to about 15% and most preferably from 5% to 10% by weight of anionic surfactants.

Other Surfactants Th· laundry detergent compositions of the present Invention may also contain cationic, anphelytlc, zwitterionic, and semi-polar surfactants ..·· Cationic detersive surfactants suitable for use 1n the laundry detergent compositions of the present Invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants Include the aaeoniua surfactants such as alkyldiaethylaemonlurn halogenldes, and those surfactants having the formula: [R2(0R3,y][R4(0R3)y]2R5ft*xwhereln Rl 1> m iiRyi or «lityl benzyl group having from about 8 to about IS carbon atone In |he alkyl chain, each R3 Is selected fro» the group consisting ef -CHgCHg-, -CHjCHICHa)-, -CH28i(CH20H}·, -CHjCHjCHg-, end mixtures thereof: each R* 1s selected fro· the group consisting of Cx-C< alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed hy joining the two R* groups, -CHgCMM-CMHCORftHOHCHzOW wherein R* It any hexose or hexoso pelyner having e eolocular weight leer than about 1000, and hydrogen when y le not 0: Rl. 1s th* same as Rt or Is an alkyl chain wherein the total nuaber of carbo* atoms of Rl plus Rs 1s net sore than about 18: each y Is fro» 0 te about 10 and the sum of the y values Is fro* 0 to about IS: and X 1s any compatible an1on~ - 18 Other cationic surfactants useful herein are also described 1n U.S. Patent 4,228,044, Cambre, issued October 14, 1980, Incorporated herein by reference.

When Included therein, the laundry detergent compositions of 5 the present invention typically comprise from OX to about 25X, preferably from about 3X to about 15X by weight of such cationic surfactants.

Ampholytlc surfactants are also suitable for use 1n 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 1n 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, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,878 to Laughlin et al., Issued December 30, 1975 at column 19, lines 18-35 (herein Incorporated by reference) for examples of ampholytlc surfactants.

When Included therein, the laundry detergent compositions of the present Invention typically comprise from OX to about 15X, preferably from about IX to about 10X by weight of such ampholytlc / surfactants.

Zwltterlonlc surfactants are also suitable for use 1n 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 et al., Issued December 30, 1975 at column 19, line 38 through column 22, line 48 (heroin Incorporated by reference) for examples of zwltterlonlc surfactants.

When Included therein, the laundry detergent compositions of the present Invention typically comprise from OX to about 15X, preferably from about IX to about 10X by weight of such zwltterlonlc surfactants.

Sem1-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 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; 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.

Semi-polar nonionic detergent surfactants Include the amine oxide surfactants having the formula 0 r3(0««)xN(R5)2 whereto R3 Is an alkyl, hydroxy al kyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R* 1s 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 R5 1s 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, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular Include Cio-Cie alkyl dimethyl amine oxides and Cg-Cig alkoxy ethyl d1hydroxy ethyl amine oxides.

When Included therein, the laundry detergent compositions of the present Invention typically comprise from 0* to about 15X, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants. - 20 Builder» 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 IX, more typically from about 5% to about 50X, preferably about 5% to about 30X, by weight of detergent builder. Granular formulations typically comprise at least about IX, more typically from about 10X to about 80X, preferably from about 15X to about 50X by weight of the 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 alkanol ammonium salts of polyphosphates (exemplified by thm tripolyphosphates, pyrophosphates, and glassy polymeric mete-phosphates), phosphonetes, phytic acid, silicates, carbonates (Including blcarbonates and sesqulcarbonates), 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 5O°C, especially less than about 4O°C. Preferred builder systems are also free of phosphate·.

Examples of silicate* builders are thm alkali metal silicates, particularly those having a SIOjtNajO ratio In the range 1.8:1 to 3.2:1 and layered silicates, such as the layered sodium silicates. - 21 Preferred crystalline layered sodium silicates have the general formula NaMSixO2x+i.yH2O 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-A3742043, 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 -, β - γ - and £ - forms of Na2Si2O5. These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is fi -Na2Si2O5, 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 sesquiIE 921961 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(zAlO2-yS1O2) wherein M 1s sodium, potassium, ammonium or substituted ammonium, z 1s from about 0.5 to about 2; and y 1s 1; this material having a magnesium Ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosilicate. Preferred-aluminosilicates are zeolite builders which have the formula: Naz[(Al02)z(S102)y]-xH20 wherein z and y are Integers of at least 6, the molar ratio of z to y 1s 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 1n structure and can be naturally-occurring alumino25 silicates or synthetically derived. A method for producing aluminosilicate 1on exchange materials Is disclosed 1n U.S. Patent 3,985,669· Krummel, 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 Ρ (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate Ion exchange material has the formula: Nai2((A102)i2(S102)i2l-xH20 wherein x Is from about 20 to about 30, especially about 27. This material 1s known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns 1n diameter. - 23 Specific examples of polyphosphates are the alkali metal tr1polyphosphates, 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 add.

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 dlphosphonlc acid e.g. the trisodium and trlpotassium salts and the water-soluble salts of substituted methylene dlphosphonlc acids, such as the trisodium and trlpotassium ethyl Idene, 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; and 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 1n the form of a neutralized salt. When utilized 1n salt form, alkali metals, such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substitute aseonlum (e.g., alkanolammonium) salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. On· Important category of polycarboxylate builders encompasses the ether polycarboxylates. A number of ether polycarboxyl ates havo been disclosed for use as detergent builders. Examples of useful ether polycarboxylates Include oxydlsuccinate, as disclosed 1n Berg, U.S. Patent 3,128,287, Issued April 7, 1984, and Lambert! et al., U.S. Patent 3,635,830, Issued January 18, 1972, both of which are Incorporated herein by reference. - 24 A specific type of ether polycarboxylates useful as builders 1n the present Invention also include those having the general formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A 1s H or OH; B 1s H or -O-CH(COOX)-CH2(COOX); and X is H or a salt-forming cation. For example, 1f 1n the above general formula A and B are both H, then the compound 1s oxydlssuccinlc acid and its water-soluble salts. If A 1s OH and B Is H, then the compound Is tartrate monosucdnlc acid (TMS, and Its water-soluble salts. If A 1s H and B 1s -0-CH(COOX)-CH2(COOX), then the compound 1s tartrate d1succ1n1c acid (TOS) and Its water-soluble salts. Mixtures of these builders are especially preferred for use herein. Particularly preferred are mixtures of TMS and TOS in a weight ratio of TMS to TOS of fro· 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 allcycllc compounds, such as those described 1n 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,(COOH,-C(R,(COOH,-0In-H wherein M Is hydrogen or. a cation wherein the resultant salt 1s water-soluble, preferably an alkali motel, ammonium or substituted ammonium cation, n 1s froa 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 1s the same or different and selected from hydrogen, Cj-4 alkyl or Cj-4 substituted alkyl (preferably R 1s hydrogen).

Still other ether polycarboxylates Include copolymers of maleic anhydride with ethyleno or vinyl methyl ether, 1, 3, 5-tr.1 hydroxy benzene-2, 4, 6-tr1sulfon1c acid, and carboxymethyl 35 oxysucdnlc acid. - 25 Organic polycarboxylate builders also Include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetlc acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetlc acid and nitrllotrlacetic acid.

Also Included are polycarboxylate» such as mellitlc acid, succinic acid, polymaleic add, benzene 1,3,5-trlcarboxyllc acid, benezene pentacarboxyl 1c add, and carboxymethyloxysuccinlc add, and soluble salts thereof.

Citric builders, e.g., citric add and soluble salts thereof, Is a polycarboxylate builder of particular importance. for heavy duty liquid detergent formulations, but can also be used 1n 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 23, 1973, Incorporated herein by reference.

Also suitable 1n the laundry detergent compositions of the present Invention are the 3,3-d1carboxy-4-oxa-l,6-hexaned1oates and the related compounds disclosed 1n U.S. Patent 4,566,984, Bush, Issued January 28, 1988, Incorporated herein by reference. Useful succinic acid builders Include the C5-C20 alkyl succinic 2S acids and salts thereof^· A particularly preferred compound of this type Is dodecenylsuccinic add. Alkyl succinic acids typically are of the general formula R-CH(C00H)CH2(C00H) 1.·., derivatives of succinic acid, wherein R 1s hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C15 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described 1n the above-mentioned patents.

The succinate builders are preferably used 1n the form of their water-soluble salts, Including the sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders Include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylIE 921961 - 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, carboxymethyl oxy sued nate, ds-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, 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 aire the polyacetal carboxylates disclosed 1n 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 glyoxyl 1c acid and a polymerization Initiator. The resulting polyacetal carboxylate ester 1s 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 art also disclosed 1n 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 adds such as maleic add, Itaconlc add, mesaconlc add, fumaric add, aconltlc add, cltraconic acid, and methylenemalon1c add.

Other organic builders known 1n the art can also be used.

For example, monocarboxylie adds, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would Include materials generally referred to es soaps. Chain lengths of C10-C20 ore typically utilized. The hydrocarbyls can be saturated or unsaturated.

Deters1ve enzymes can bo Included In the laundry detergent compositions of the present Invention for e variety of reasons - 27 including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be Incorporated Include proteases, amylases, Upases, 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 1s governed by several factors such as pH-actlvity and/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 subtil Bins which are obtained from particular strains of B.subtil 1s and B.llchenlforms. 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. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available Include those sold under the tradenames ALCALASE?** and SAVINASE™ by Novo Industries A/S (Denmark) and MAXATASE™ by International B1o-Synthet1cs, Inc. (The Netherlands).

Of Interest In the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein ae Protease A and Protease B. Protease A and methods for Its preparation are described In European Patent Application 130,758, published January 9, 1985, Incorporated herein by reference. Protease 8 Is a proteolytic enzyme which differs from Protease A 1n that 1t has a leucine substituted for tyrosine 1n position 217 1n Its amino add sequence. Protease B 1s described In European Patent Application Serial No. 87303761.8, filed April 28, 1987, Incorporated herein by reference. Methods for preparation of Protease B are also disclosed 1n European Patent Application 130,756, Bott et al., published January 9, 1985, Incorporated herein by reference. - 28 Amylases Include, for example, β-amylases obtained from a special strain of B.llcheniforms, described 1n more detail in British patent specification No. 1,296,839 (Novo,, previously incorporated herein by reference. Amylolytic proteins Include, for example, RAPIDASE™, International B1o-Synthet1cs, Inc. and TERMAMYL™, Novo Industries.

The celluloses 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 celluloses are disclosed 1n U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, Incorporated herein by reference, which discloses fungal cellulase produced from Humicola 1nso1ens. Suitable cellulases are also disclosed 1n G8-A-2.075.028; G8-A-2.095.275 and DE-OS-2.247.832.

Examples of such celluloses are celluloses produced by a strain of Humicola Insolent (Huaicole grlsea var. thermoidea), particularly the Humicola strain DSN 1800, and celluloses produced by a fungus of Bacillus N or e cellules· 2l2-produc1ng fungus belonging to the genus Aeromonas, and cellulose extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).

Suitable lipase enzymes for detergent usage Include those produced by microorganisms of th· Pseudomonas group, such as Pseudomonas stutzerl ATCC 19.154, as disclosed In British Patent No. 1,372,034, Incorporated herein by referenc·. Suitable Upases Includ· those which shoif · positive Immunological cross-reaction with th· antibody of the lipas·, produced by the microorganism Pseudomonas fluorwns IAH 1057. This Upas· and a method for Its purification hav· boon described In Japanese Patent Application No. 53-20487, laid open to public Inspection on February 24, 1978. This lipase 1s available from Amano Pharmaceutical Co. Ltd., Nagoyt, Japan, under the trade name Lipase P Amano,* hereinafter referred to as Amano-P. Such Upases of the present Invention should show a positive Immunological cross reaction with the Amano-P antibody, using tho standard and well-known immunodiffusion procedure according to Ouchtsrlony (Acte. Med. Scan., 133, pages 78-79 (1950)). Those - 29 Upases, and a method for their Immunological cross-reaction with Amano-P, are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987, incorporated herein by reference. Typical examples thereof art tho Amano-P llpast, tho lipase ex Pstudoaonu frtgl PERM P 1339 (available under the trade name Amano-B), lipase ex Psutdoaonts nitrortductns var. Ifpolyticua FERN P 1338 (available under tho trade name Amano-CES), lipases ex Chroaobtcttr vlscasua, e.g. CAreaobecter viscosua var. lipolytlcua NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chroaobtcter v/scosum Upases from U.S. Biochemical Corp., U.S.A. and Olsoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. An especially preferred lipase enzyme 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 art-used in combination with oxygon source·, e.g., percarbonat·, perborate, persulfate, hydrogen peroxide, etc. They art used for solution bleaching, 1.a. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates 1n the wash solution. Peroxidase enzymes are known In the art, and Include, for example, horseradish peroxidase, ligninase, and haloperoxldase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example· In PCT International Application HO 89/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries VS, Incorporated herein by reference.

A wide range of enzyme eater Isis and eoane for their Incorporation Into synthetic detergent granules Is also disclosed In U.S. Patent 3,553,139, Issued January 9, 1971 te NcCarty et al. (Incorporated herein by reference)· Enzymes are further disclosed In U.S. Patent No. 4,101,457, Place et al.. Issued July 18, 1978, and 1n U.S. Patent 4,507,219, Hughes, Issued March 26, 1985, both Incorporated heroin by reference· Enzyme materials useful for liquid detergent formulations, and their Incorporation Into such formulations, are disclosed 1m U.S· Patent 4,281*868, Hora at al.. Issued April 14, 1981, also Incorporated herein by reference.

Enzymes are noreally incorporated at levels sufficient to 3S provide up te about 5 ng by weight, mem typically about 0.05 mg to about 3 ng, of active enzyme per gras of the composition.

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 1n the art. For example, one technique for enzyme stabilization 1n 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 1n 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 (e.g., alkanolamlnes such as diethanolamine, triethanolamine, d1-Isopropanol amine, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified 1n U.S. Patent 4,281,868, Issued April 14, 1981 to Hom, 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, 1986, Venegas. Non-bor1c acid and borate stabilizers: are preferred. Enzyme stabilization systems are also described, for example, 1n U.S. Patents 4,261,868, 3,600,319, and 3,519,570.

Bleaching Compounds - Bleaching Aoents and Bleach Activators The laundry detergent compositions of the present Invention may 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 IX to about 20X, more typically from about IX to about 10X, of such laundry detergent composition. In general, bleaching compounds are optional components in non-11qu1d formulations, e.g., granular detergents. If present, the amount of bleach activators will - 31 typically ba from about 0.1% to about 80%, nor· 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 cleanlngi purposes that are now known or become known.

One category of bleaching agent that can be used encompasses percarboxylle add bleaching agents and salts thereof. Suitable examples of this class of agents Include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chioro perbenzole add, 4-nonylam1no-4-oxoperoxybutyr1c add and dlperoxydodecanedlole acid. Such bleaching agents are disclosed In U.S. Patent 4,483,781, Hartman, Issued November 20, 1984, U.S. Patent Application 740,448, Bums et el., filed Juno 3, 1985, European Patent Application 0,133,358, Banks et el., published February 20, 1985, and U.S. Patent 8,412,938, Chung et al.. Issued November 1, 1983, ell of which am Incorporated by reference herein/Highly preferred bleaching agents also Include 8-nonylamlno-8-oxoperoxycapmlc add as described In U.S. Patent 4,834,551, Issued January 9, 1987 to Bums, 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 NaBO2H2O2 or tetrahydrate NaBO2H2O2.3H2O.

Sodium percarbonate, which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene, - 32 IE 921961 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:Na2O 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 5%) of silicate 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 (i.e., 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).

H R - C - L wherein λ Is an alkyl group containing fro· about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and Including the carbonyl carbon contains from about 5 to about 10 carbon atoms and L 1s a leaving group, the conjugate acid of which has e pK« In the range of fro· about 4 to about 13. These bleach activators art described 1n U.S. Patent 4,915,854, Issued April 10, 1990 to Mao, et el.. Incorporated herein by reference, end U.S. Patent 4,412,934, which was previously Incorporated herein by reference.

Bleaching agents other thm oxygen bleaching agents are also known In the art and cm bu utilized herein. One type of nonoxygen bleaching agent of particular Interest Includes photoactlveted bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials cm be deposited upon the substrate during the washing process. Upon Irradiation with light, in the presence of oxygen, such es by hanging clothes out to dry In the daylight, thm sulfonated zinc phthalocyanlne 1s activated and, consequently, the substrate Is bleached. Preferred - 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 0.025X 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 1n the laundry detergent compositions of the present Invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophUlze 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, 1975 to Nicol, et al., Incorporated herein by reference.

Soil release agents characterized by poly(vinyl ester) hydrophobe segments Include graft copolymers of poly(vlny) ester), e.g., Ci-C« vinyl esters, preferably poly(v1nyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. Such materials are known 1n 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 Sokalan™ type of material, e.g., Sokalan™ HP-22, available from BASF (West Germany).

One type of preferred soil release agent 1s a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More 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 1s 1n the range of froa about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, Issued May 25, 1976, which 1s Incorporated by reference. See also U.S. Patent 3,893,929 to Besadur Issued July 8, 1975 (Incorporated by reference) which discloses similar copolymers.

Another preferred polymeric soil release agent 1s 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 froa a polyoxyethylene glycol of average Molecular weight 300-5,000, and the aole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units In the polymeric compound 1s between 2:1 and 6:1. Examples of this polymer Include the commercially available material Zelconl 5126 (from Dupont) and MlleaseR T (froa ICI). These polyaers and Methods of their preparation are eore fully described In U.S. Patent 4,702,857, Issued October 27, 1987 to 6osse11nk, which Is Incorporated herein by reference.

Another preferred polyaerlc soil release agent is a sulfonated product of e substantially linear ester oligomer comprised of an ollgoaerlc ester backbone of terephthaloyl and oxyalkyleneoxy repeat unit» and terminal moieties covalently attached to the backbone, said soil release agent being derived - 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 November 1990 to J. J. Schelbel and Ε. P. Gossellnk, 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-polyoxy10 ethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gossellnk et al., the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, Issued January 26, 1988 to Gossellnk, 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 Gossellnk, having polyethoxy end-caps of the formula X-(OCH2CH2)n- wherein n 1s from 12 to about 43 and X 1s a C1-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 4,877,898, 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 unsymmetrlcally substituted oxy-1,2-alkyleneoxy units.

If utilized, soil release agents will generally comprise from about 0.01* to about 10.OX, preferably from about 0.1X to about 5.OX,.more preferably fro· about 0.2X to about 3.OX by weight of th· laundry detergent compositions of the present Invention.

Chelating Aoents The laundry detergent compositions 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 fro· the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter - 36 defined. Without Intending to be bound by theory, it is believed that the benefit of these materials 1s due 1n 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 - CHg \ N - (CH2)x - COOH, / wherein H 1s hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x Is from 1 to about 3, preferably 1. Preferably, these amino carboxylates do not contain j5 alkyl or alkenyl groups with more than about 6 carbon atoms.

Operable amine carboxylates Include ethylenedlamlnetetraacetates, N-hydroxyethylethylenedlamlnetrlacetates, nitri1otr1acetates, ethylenediamine tetraproprlonates, triethylenetetraaminehexaacetates, diethylenetrlamlnepentaacetates, and ethanoldlglydnes, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonetes are also suitable for use as chelating agents In the laundry detergent compositions of the present Invention when at least Io* levels of total phosphorus are permitted In detergent compositions. Compounds with one or more, preferably at least two, units of the substructure - CH{ \ N - (CH2,x - PO3M2, / wherein N Is hydrogen, alkali metal, ammonium or substituted ammonium and x 1s from 1 to about 3, preferably 1, art useful and Include ethylenedlamlnetetrakls (methylenephosphonates), nltrllotrls (methylenephosphonates) and diethylanetrlamlnepentakis (methylenephosphonates). Preferably, these amino phosphonetes do ,E 921961 - 37 not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally-subst1tuted aromatic chelating agents are also useful 1n the compositions herein. These materials can comprise compounds having the general formula wherein at least one R Is -SO3H or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, Issued Hay 21, 1974, to Connor et al., Incorporated herein by reference, discloses polyfunctionally - substituted aromatic chelating and sequestering agents. Preferred compounds of this type 1n add form are dihydroxydlsulfobenzenes such as 1,2-41hydroxy-3,5-d1sulfobenzene. Alkaline detergent compositions can contain these materials 1n the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or tr1ethanol-amine) salts.

If utilized, these chelating agents will generally comprise from about 0.1X to about 10X by weight of the laundry detergent compositions of the present Invention. More preferably chelating agents will comprise from about 0.1X to about 3.OX by weight of such compositions.

Clav Soil Removal/Anti-redeoosltlon Agents Clay soil removal/antl-redeposition agents useful 1n the laundry detergent compositions of the present Invention Include polyethylene glycols and water-soluble ethoxylated amines having clay soil removal and ant1-redepos1t1on properties.

Polyethylene glycol compounds useful in the laundry detergent compositions of the present Invention typically have a molecular weight 1n 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 ΙΟ - 38 Carbowax·, which 1s available from Union Carbide, located in Danbury, Conn.

The water-soluble ethoxylated amines are preferably selected from the group consisting of: (1) ethoxylated monoamines having the formula: R2-N-Rl-|i|-R2 (R2j2-N-I|1-N-(R2)2 L L L ι I t XX X or (X-l-)2-N-Rl-N-(R2)2 (3) ethoxylated polyamines having the formula: R2 R3-[(*l),-(R<)t-N-L-X]p (4) ethoxylated amine polymers having the general formula: R2 ((r2)2-n}w{r1-n]x{r1-n},(r1-n-l-X)z L ι X and (5) mixtures thereof; wherein Al 1s 0 0 Q 0 II ll ll Η H -NC-, -NC0-, -NCN-, -CN-, -OCN-, R R R R ' R R 0 0 0 0 II II (I ii ·· -CO-, -0C0-, -0C-, -CNC-, R or -0-; R Is H or C1-C4 alkyl or hydroxyalkyl; R1 Is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having fro» 2 to about 20 oxyalkylene units provided that no O-N bonds arm formed; each R2 Is C1-C4 or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r, -A2-(CH2)j-, wherein A2 1s -0- or -CH2-, r is 1 or 2, s Is 1 or 2, and r + s is 3 or 4; X Is a nonionic group, an anionic - 39 group op mixture thereof; r3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or 0-N bonds are formed; L 1s a hydrophilic chain which contains the polyoxyalkylene moiety -E(R5O}B,(CH2CH2O)n]-, wherein R5 1s C3-C4 alkylene or hydroxyalkylene and n and n are numbers such that the moiety -(CH2CH2O)n- comprises at least about SOX by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and n 1s at least about 12; for said diamines, m 1s from 0 to about 3, and n Is at least about 6 when Ri 1s C2-C3 alkylene, hydroxyelkylene, or alkenylene, and at least about 3 when Ri is other then C2-C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m Is from 0 to about 10 and n 1s at least about 3; p Is from 3 to 8; q 1s 1 or 0; t 1s 1 or 0, provided that t 1s 1 when q 1s 1; w is 1 or 0; x + y + z 1s at least 24 and y + z 1s at least 2. The most preferred soil release and anti-redeposition agent Is ethoxylated tetraethylenepentamlne.

Exemplary ethoxylated amines are further described 1n U.S. Patent 4,597,898, VanderMeer, Issued July 1, 1988, Incorporated herein by reference. Another group of preferred clay soil removal/antlredeposltlon agents are the cationic compounds disclosed 1n European Patent Application 111,955, Oh and Gossellnk, published June 27, 1984, Incorporated herein by reference. Other clay soil removal/antl-redeposltlon agents which can be used Include the ethoxylated amine polymers disclosed In European Patent Application 111,984, Gossellnk, published June 27, 1984; the zwltterlonlc polymers disclosed 1n European Patent Application 112,592, Gossellnk, published July 4, 1984; and the 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 ant1-redepos1t1on agents are ethoxylated tetraethylenepentamlne and the polyethylene glycols having a molecular weight 1n the range of from about 4,000 to about 8,000. - 40 Granular detergent compositions which contain such compounds typically contain from about 0.01% 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 1n the laundry detergent compositions of the present Invention. These materials can aid 1n calcium and magnesium hardness control. In addition to acting as a builder adjunct analogously to the polycarboxylate described above in the Builder description, 1t 1s believed, though 1t 1s 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 antlredepositlons, when used 1n 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 contain at least about 60% by weight of segments formula Z I . C III I COOM n wherein X, Y, and Z are each selected froa the group consisting of hydrogen, methyl, carboxy, carboxyaethyl, hydroxy and hydroxy30 aethyl; a salt-forming cation and n Is froa about 30 to about 400. Preferably, X Is hydrogen or hydroxy, Y Is hydrogen or carboxy, Z Is hydrogen and M 1s hydrogen, alkali metal, ammonia or substituted unonlua.

Polyaerlc polycarboxylate materials of this type can be prepared by polymerizing or copolyaerlzlng suitable unsaturated monomers, preferably in their acid fora. Unsaturated monomeric copolymers which with the general ~ X I I Y - 41 acids that can be polymerized to form suitable polymeric polycarboxylates Include acrylic acid, maleic acid (or maleic anhydride,, fumaric acid, 1tacon1c add, aconltlc add, mesaconic add, dtraconlc add and methylenemalon 1c add. 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 add. Such acrylic add-based polymers which are useful herein are the water-soluble salts of polymerized acrylic add. The average molecular weight of such polymers in the add 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 ,000. Water-soluble salts of such acrylic add homopolymers can Include, for example, the alkali metal, ammonium and substituted aoeonlum salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type 1n detergent compositions has been disclosed, for example, in Diehl, U.S.

Patent No. 3,308,067, Issued March 7, 1967. This patent 1s Incorporated herein by reference.

Acryllc/melelc-based copolymers may also be used as a preferred component of the dispersing agent. Such materials include tho water-soluble silts of copolymers of acrylic acid and maleic acid. Tho averagg molecular weight of such copolymers 1n the add form ranges fro· about 5,000 to 100,000, preferably from about 6,000 to 60,000, more preferably from about 7,000 to 60,000.

Th· ratio of acrylate to maleate segments 1n such copolymers will generally rang· fro· about 30:1 to about 1:1, aoro preferably fro· about 10:1 to 2:1. Wator-solubl· salts of such acrylic add/ maleic acid copolymers can Includ·, for example, tho alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this typo art known materials which are described In European Patent Application No. 66915, published Oecember 15, 1982, which publication 1s Incorporated heroin by reference. - 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. Brlahisnsr Optical brighteners or other brightening or whitening agents known to those skilled 1n the art can be incorporated Into the laundry detergent compositions of the present Invention. However, the choice of brlghtentr will depend upon a number of factors, such as the type of detergent, the nature of other components present 1n the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.

The brlghtener selection Is also dependent upon the type of material to be cleaned, e.g., 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 e variety of fabrics. It 1s of course necessary that the Individual components of such a brlghtener mixture be compatible.

Commercial optical brighteners can be classified Into subgroups which Include, but are not necessarily limited to, derivatives of stilbene, pyrazollne, coumarin, carboxylic acid, methInecyanines, d1benzoth1phene-5,5-d1ox1de, azoles, 5- and 6-membered-rlng heterocycles, and other miscellaneous agents.

Examples of such brighteners are disclosed 1n The Production and Application of Fluorescent Brightening Agents, M. Zahradnik, Published by John Wiley 8 Sons, New York (1982), the disclosure of which Is Incorporated herein by reference.

Stilbene derivatives Include, but are not necessarily limited to, derivatives of b1s(triazinyl)amino-stilbene; bisacyl amino derivatives of stilbene; triazole derivatives of stilbene; oxadlazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Certain derivatives of bis(triazinyl)aminostilbene may be prepared from ♦,4'-d1amine-stilbene-2,2'-d1sulfon1c add.

IE 921961 - 43 Coumarin derivatives include, but are not necessarily limited to, derivatives substituted in the 3-position, 1n the 7-position, and In the 3- and 7-positions.

Carboxylic acid derivatives include, but are not necessarily 5 limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-b1s-acryl1c acid derivatives; naphthalenedlcarboxyl1c acid derivatives; heterocyclic add derivatives; and cinnamic acid derivatives.

Cinnamic add derivatives can b« further subclassified into 10 groups which Include, but are not necessarily limited to, cinnamic add derivatives, styrylazoles, styryl benzofurans, styryloxadlazoles, styryltrlazoles, and styryl polyphenyls, as disclosed on page 77 of the Zahradnlk reference.

The styrylazoles can be further subclassified Into styryl 15 benzoxazoles, styryl Imidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnlk 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 d1benzoth1ophene-5,S-d1ox1de disclosed at page 741-749 of lbs Kirk-Othmer Encyclopedia of Chemical Technology. Volume 3, pages 737-750 (John Miley & Son, Inc., 1982), the disclosure of which 1s Incorporated herein by reference, and Include 3,7-d1an1nod1benzoth1ophehe-2,8-d1sulfon1c add 5,5 dioxide.

Other optical brighteners are azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcategorized Into nonoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed 1n the Kirk-Othmer reference.

Still other optical brighteners are the derivatives of 6-membered-r1ng heterocycles disclosed 1n the Kirk-Othmer reference. Examples of such compounds Include brighteners derived from-pyraz1ne and brighteners derived from 4-an1nonaphthalam1do.

In addition to the brighteners already described, miscellaneous agents may also bo useful as brighteners. Examples - 44 of such miscellaneous agents are disclosed at pages 93-95 of the Zahradnlk reference, and Include l-hydroxy-3,5,8-pyrenetrisulfonlc add; 2,4-d1methoxy-l,3,5-tr1az1n-6-y1-pyrene; 4,5-diphenylImidazolonedlsulfonic acid; and derivatives of pyrazoline5 quinoline.

Other specific examples of optical brighteners are those identified 1n U.S. Patent 4,790,855, issued to Wixon on Oecember 13, 1988, the disclosure of which is Incorporated herein by reference. These brighteners Include the Phorwhlte™ series of brighteners from Verona. Other brighteners disclosed 1n this reference Include: T1nopal UNPA, TInopal CBS and Tlnopal 5BM; available from C1ba-Ge1gy; Arctic White CC and Artie White CWO, available from H1lton-0av1s, located In Italy; the 2-(4-styrylphenyl)-2H-naphthol[l,2-d]tr1azoles; 4,4'-b1s-(l,2,3-tr1azol-215 yl)-stilbenes; 4,4'-b1s(styry1)b1spheny1s; and the y-amlnocoumarlns. Specific examples of these brighteners Include 4-methyl-7-d1ethylamino coumarin; l,2-b1s(-benz1m1dazol-2-yl)ethylene; l,3-d1phenylphrazo11nes; 2,5-b1s(benzoxazol-2-yl)thlophene; 2-$tyryl-naphth-[l,2-d]-oxazo1e; and 2-(stllbene-4-yl)20 2H-naphtho[l,2-d]tr1azo1e.

Still other optical brighteners Include those disclosed 1n U.S. Patent 3,645,015, Issued February 29, 1972 to Hamilton, the disclosure of which Is incorporated herein by reference.

If utilized, the optical brighteners will generally comprise from about 0.05» to about 2.OX, preferably from about 0.1X to about 1.0X by weight of the laundry detergent compositions.

Sudi Superman Compounds known, or which become known, for reducing or suppressing the formation of suds can be incorporated into the laundry detergent compositions of the present Invention. The incorporation 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 - 45 surfactant. Suds suppression 1s 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 1n the art. They are generally described, for example. In Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley 4 Sons, Inc., 1979). One category of suds suppressor of particular Interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed 1n 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 alkanol ammonium 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 (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cig-C4o ketones (e.g. stearone), etc. Other suds Inhibitors Include N-alkylated amino triazines such as tri- to hexa-alkyl melamines or d1- to tetra-alkyldiamine chiortrlazines formed as products of cyanurlc 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 - 46 monostearyl d1-alkal1 metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters. The hydrocarbons, such as paraffin and haloparaffln, 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 110'C (atmospheric pressure). It 1s also known to utilize waxy hydrocarbons, preferably having a melting point below about 100'C. 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 polyorganoslloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganoslloxane oils or resins, and combinations of polyorganoslloxane with silica particles wherein the polyorganoslloxane 1s chemisorbed of fused onto the silica.

Silicone suds suppressors art 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. S., both incorporated herein by reference.

Other si1 leone 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 polydlmethylslloxane fluids.

Mixtures of silicone and sllanated silica are described, for Instance, 1n German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents 1n granular detergent - 47 compositions are disclosed 1n U.S. Patent 3,933,672, Bartolotta et al., and 1n U.S. Patent 4,652,392, Baglnskl 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: (1) polydimethyl siloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25*C; (11) from about 5 to about 50 parts per 100 parts by weight of (1) of siloxane resin composed of (043)3 5101/2 units of SIO2 units in a ratio of from (€(13)3 SIO1/2 units and to SIO2 units of from about 0.6:1 to about 1.2:1; and (111) from about 1 to about 20 parts per 100 parts by weight of (1) of a solid silica gel; Suds suppressors, when utilized, are present 1n a suds suppressing amount. By suds suppressing amount 1s 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 1s used to achieve the desired suds control then 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, monocarboxyl 1c fatty acids, and salts, thereof, will be present typically In amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor 1s utilized. Silicone suds suppressors are typically utilized 1n amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit 1s practical 1n 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 - 48 silicone suds suppressor 1s used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values Include any silica that may be utilized 1n combination with polyorganoslloxane, 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 S.0%, although higher levels can be used.

Other Ingredients A wide variety of other Ingredients which can be included 1n 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 iso20 propanol are suitable. Monohydrlc 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 (0.9., propylene glycol, ethylene glycol, glycerine, and l,3-propaned1ol) can also be used.

The laundry detergent compositions of the present Invention will preferably be formulated such that during use 1n aqueous cleaning operations, the wash water will have a pH of between about 5.5 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 1n 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 - 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 1s 1n the range of from about 1:5 to about 5:1, In the presence of a solvent such as water or a water-mi sdble solvent (e.g., 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.

EXPERIMENTAL This exemplifies a process for making e N-methyl, 1-deoxyglucityl lauramlde surfactant for use herein. Although a skilled chemist can vary apparatus configuration, on· suitable apparatus for use herein comprises a three-11ter four-necked flask fitted with e motor-driven paddl· stirrer and a thermometer of length sufficient to contact th· reaction medium. Th· other two necks of the flask ar· fitted with a nitrogen sweep and a wide-bora sidearm (caution: a wlde-bore side-arm Is Important 1n 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 end vacuum gauge, then to en aspirator and a trap. A 500 watt heating mantle with a variable transformer temperature controller (Varlac) used to heat the reaction Is so placed on a lab-jack tha£ 1t may be readily raised or lowered to further control temperature of the reaction.

N-methylglucamlne (195 g., 1.0 mole, Aldrich, H4700-0) and methyl laurate (Proctor λ Gamble CE 1270, 220.9 g., 1.0 mole) are placed 1n a flask. The sol1d/l1quid mixture 1s heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes). When the melt temperature reaches 145* C, catalyst (anhydrous powdered sodium carbonate, 10.5 g., 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 1s held at - 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 1s distilled over until Its rate subsides. The vacuum 1s 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 1s 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. - 51 In the Examples, the abbreviated component identifications have the following meanings: C12LAS Sodium linear C12 alkyl benzene sulfonate TGA Glucityl tallow fatty acid amide TAS Sodium tallow alcohol sulfate C14/15AS Sodium C14-C15 alkyl sulfate C12/15AE3S Sodium Ci2"Ci5 alkyl ether sulfate containing an average of three moles of ethylene oxide per mole of alkyl sulfate TAEn Tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol. 45E7 A C 14_15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide. 25E3 A Ci2Cl5 primary alcohol condensed with an average of 3 moles of ethylene oxide. TAED Tetraacetyl ethylene diamine Silicate Amorphous Sodium Silicate (SiO2:Na2O ratio normally follows). Carbonate Anhydrous sodium carbonate CMC Sodium carboxymethyl cellulose Zeolite A Hydrated Sodium Aluminosilicate of formula Nai2(AlO2SiO2)l2-27H2O having a primary particle size in the range from 1 to 10 micrometers Citrate Tri-sodium citrate dihydrate MA/AA Copolymer of 1:4 maleic anhydride/acrylic acid, average molecular weight about 80,000. - 52 Perborate Monohydrate Enzyme Brightener: DETPMP SUDS Suppressor Anhydrous sodium perborate bleach empirical formula NaBO2-H2O2 Mixed proteolytic and amyloytic enzyme sold by Novo Industries AS. Disodium 4,4*-bis(2-morpholino-4aniIino-s-triazin-6-ylamino)stilbene2:2'-disulphonate.

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

Example I The following particulate detergent compositions were prepared: TAS A 2.43 C14/15AS 5.4 C12/15AE3 S 1.5 TGA 3.5 25E3 3.0 Zeolite A 15.0 Citrate 6.5 Silicate (2.0 ratio) 3.5 Carbonate 13.6 MA/AA 4.25 DETPMP 0.38 CMC 0.48 TAEp 5.0 Perborate 16.0 Enzyme 1.4 Brightener 0.19 Suds Suppressor 3.0 6.5 6.5 The Performance of the three compositions was compared in both Tergotometer Tests and in full scale washing machine tests.

Tergotometer Tests 6x2 litre metal pots were filled with water of 12° 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 0.7%. 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 Scheffe scale. - 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: greasy stains on cotton (lipstick, DMO). 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.

Tergotometer A/B A/C Cotton - sebum -0.3 -0.3 - polish +0.6 +0.2 -DMO + 1.1(5) +0.8 Polycotton - sebum +0.2 +0.4 - polish +0.8 +0.5 -DMO + 1.5(s) +0.5 Washing Machine Lipstick/Cotton + 1.5(s) +0.2 DMO/cotton + 1.2- +0.5 Makeup/polyester + 1.0 +0.3 Polish/polyester + 1.4(s) + l.l(s) (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. - 56 Example Π Composition A of Example I was compared to a commercially available detergent composition (D) 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 % ΤΑΕι μ 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 expert panel using a five point Scheffe scale showed that Composition A provided a stain removal benefit over Composition D of > 2 psu on polish froiJi polyester > 1 psu on DM0 from polycotton >1.5 psu on make up from cotton I - 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 C16-C18 predominantly linear primary alcohols condensed with an average of three and five moles of ethylene oxide respectively. The performance comparisons were made 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 Scheffe'scale 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.

Polycotton A/D A/E - Sebum +0.8s +0.3 - polish -0.3 -0.6 -DMO + 1.8s +2.0s Polyester - sebum +2.6s +2.7s - polish + 1.6s +0.5 -DMO +0.8s + 1.5s s= statistically significant at 95% confidence level

Claims (2)

1.) A laundry detergent composition useful for cleaning fabrics in automatic washing machines, said composition comprising one or more water soluble anionic, cationic, ampholytic or zwitteronic detersive surfactants or mixtures thereof, and optionally detergent builder compounds, said composition being characterised in that it comprises, in combination, (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having the formula G Ri r 2 —C-N—Z where Ri is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R 2 is C5-C31 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 (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. 2. ) A laundry detergent composition according to claim 1 wherein component a) is a polyhydroxy fatty acid amide of formula O Ri R 2 — C — N —CH2(CHOH)4CH 2 OH wherein R 2 is a C11-C19 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-C19 straight chain alkyl or alkenyl group or a mixture thereof and Ri 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. 5. ) 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 (a) and from 1% to 10% of component (b), 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. 7. ) A granular laundry detergent composition according to claim 6 wherein the anionic surfactant comprises watersoluble Ci2-Cig alkyl sulfates, Cx 2 -Ci8 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 C14-C15 alkyl sulfate and a minor proportion, by weight of the mixture, of a Ci 2 C15 alkyl ethoxy sulfate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. 10. ) 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. - 61 1

2.) A laundry detergent composition according to claim 1, substantially as hereinbefore described and exemplified.