CA2233474A1

CA2233474A1 - Stable, aqueous laundry detergent composition having improved suspension properties

Info

Publication number: CA2233474A1
Application number: CA 2233474
Authority: CA
Inventors: Francesco De Buzzaccarini; Yueqian Zhen
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1995-09-29
Filing date: 1996-09-27
Publication date: 1997-04-03
Also published as: EP0854906A1; WO1997012019A1; AR003724A1; JPH11512768A; BR9611141A

Abstract

Heavy duty liquid detergent compositions containing an anionic surfactant component and a quaternary ammonium surfactant are disclosed. The anionic surfactant component comprises, by weight of the composition, from about 5 %
to 40 % of alkyl sulfates or alkyl polyethoxylate sulfates. The compositions are structured, provide excellent cleaning of soils, excellent softening, and are capable of suspending particles of up to about 200 microns for at least about one month.

Description

W O 97/12019 PC~US96J15522 I

STABLE, AQUEOUS LAUNDRY DETERGENT COMPOSITION HAVING IMPROVED SUSPENSION
PROPERTIES

TECHNICAL FIELD
The present invention relates to stable, aqueous heavy duty liquid laundry detergent compositions comprising anionic surfactants and cationic surfactants in a specific ratio to provide exceptional cleaning and softening benefits. Moreover, the detergent compositions herein are structured and have strong suspension properties.
The anionic surfactant component comprises alkyl sulfates and alkyl ethoxylated sulfates.
BACKGROUND OF THE INVENTION
Numerous ~ have been made in the past to formulate laundry detergent compositions which have good clezlning properties and which are capable of suspending particles. However, such liquid deleLgelll compositions present nurnerous problems to the forrnnl~tor, including high viscosity at pouring shear rate, insufficient ability to suspend particles, instability during storage, and undesirable appearance.
Attempts to formulate liquid laundry detergent compositions capable of suspending solids in the past have included the use of clays or polymers which act to forrn a shear thinning composition. While these compositions are capable of suspending particles, many have been found to have poor physical product characteristics, including phase split. Moreover, forrn~ tors were limited to a small selection of suitable d~ c;--l ingredients in relatively low concentrations.
It has now been found that aqueous, heavy duty liquid del~ llL compositions CO~ certain anionic s~ rt~nt~ and ~ y ammonium surfactants provide excellent cleaning p~lro....~nce, softening benefits, and attractive product characteristics, i.e., are structured, phase stable, and have a rheology which allows for the suspension of particles while being easy to pour from the product container.
Without being limited by theory, it is believed that these novel compositions have an intlorn~l structure which comprises liquid crystalline surfactant particles, also known as lamellar droplets. These particles are dispersed in the aqueous phase and are capable of suspending solids. Lamellar droplets are known in the art, e.g., H. A. Barnes, "Detergents", in K. Walters (Ed), "Rheometry: Industrial Applications", J. Wiley & Sons, Lt;lchw~,llh 1980. The presence of such surfactant droplets or particles in d~ nt compositions may be determined by optical means W O 97/12019 PCT~US96/155Z2 or by electronic microscope, such as a k~n~mi~ion or sc~nnin~ electron microscope.
Therefore, it is an object of the invention herein to provide a structured, aqueous heavy duty liquid laundry detergent composition which provides excellentcleaning and softening benefits and a desirable rheology.
BACKGROUND ART
Cationic surfactants, including q~ tt~ ry ammonium surfactants, have long been known as useful additives in laundry detergent compositions for the purpose of providing laundered fabrics with a static control benefit (see e.g. U.S. Patent No.
3,951,879, Wixon, issued April 20, 1976, and U.S. Patent No. 3,9~9,157, Inamorato, issued May 25, 1976, both of which are incorporated herein by reference), a fabric softening benefit (see e.g., U.S. Patent No. 3,607,763, Salmen et al, issued September 21, 1971, U.S. Patent No. 3,644,203, Lamberti et al, issued February 22, 1972, and U.S. Patent No. 3,537,993, Coward et al, issued November 3, 1970, all of which are incorporated herein by reference), or a sanitation benefit (see e.g., U.S.
Patent No. 2,742,434, Kopp, issued April 17, 1956, U.S. Patent No. 3,539,520, Cantor et al, issued November 10, 1970, and U.S. Patent No. 3,965,026, Lancz, i-ssued June 22, 1976, all of which are inco,~oldled herein by reference).
SUMMARY OF THE INVENTION
The present invention encomp~ses a structured, heavy duty liquid laundry detergent compositions comprising, by weight of the composition:
a) from about 10% to about 40% of an anionic surfactant conlpollellt which comprises, by weight of the composition:
(i) from about 5% to about 40% of alkyl sulfate or alkyl polyethoxylate sulfates wherein the alkyl group contains from about 10 to about 22 carbon atoms and the polyethoxylate chain contains from 0 to about 15, preferably from 0 to about 5, more preferably from 0 to about 4, ethylene oxide moieties; and (ii) no more than about 5% of fatty acids;
b) from about 1% to about 10% of a qU~t~rn~ry ammonium surfactant having the formula R4~ ~ R1 N X e - R3 R2_ wherein R1 and R2 are individually selected from the group consisting of C1-C4 alkyl, Cl-C4 hydroxy alkyl, benzyl, and -(C2H4O)XH where x has a value from about 2 to about 5; X is an anion; and (1) R3 and R4 are each a WO 97/12019 PCT~US96~1~522 C6-C14 alkyl or (2) R3 is a C6-C1g alkyl, and R4 is selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 hydroxy alkyl, benzyl, and (C2H40)XH where x has a value from 2 to 5;
c) no more than about 10%, by weight, of solvents or hydrotropes; and d) from 0% to about 10% of a suitable electrolyte or acid equivalent thereof;
provided that the weight ratio of anionie surfactant to qu~tern~ry ammonium surfactant is from about 1.5:1 to about 5:1; and wherein said anionic and qn~tern~ry ammonium surfactants form liquid crystalline particles.
The compositions herein have a viscosity at 20 s-l shear rate of from about 100 cp to about 4,000 cp, preferably from about 100 cp to about 2,000 cp, more preferably from about 200 cp to about 1,000 cp and are stable upon storage.
All percentages and proportions herein are by weight, and all references cited are hereby incorporated by referenee, unless otherwise specifically indicated.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, it has now been found that a stable, aqueous heavy duty liquid d~L~ lL eomposition is surprisingly formed when certain anionic surfactants and a qn~tern~ry ammonium surfactants are combined in relative proportions specified hereinafter.
The compositions herein are structured and have a specific rheology. The rheology can be modeled by the following formula:
o + Ky(n~l) where T~ is the viscosity of the liquid at a given shear rate, r~O is the viscosity at infinite shear rate, y is the shear rate, n is the shear rate index, and K is the con~i~tçn-y. As used herein, the term "structured" inc1ieatl~ a heavy duty liquid eomposition having liquid erystalline surfaetant partieles and an infinite shearViSCQsity (T~o) value between O and about 3,000cp (eentipoise), a shear index (n) value of less than about 0.6, a eon~isteney value, K, of above about 1,000, and a viscosity (rl) measured at 20-1 of less than about lO,OOOep, preferably less than about S,OOOcp. Under low stress levels, a "zero shear" viscosity is above about lOO,OOOcpwherein"zeroshear" ismeantashearrateofO.OOl s-l orless. Theyield value of the eompositions herein, obtained by plotting viscosity versus stress, is larger than 0.2Pa. These rheology parameters can be measured with any commercially available rheometer, such as the C~rrime~l CSL 100 model.
The struetured compositions herein are eapable of suspending insoluble partieles whieh ean be in a solid, liquid, or liquid crystalline phase. By "suspending" is meant the ability to avoid settling or physical separation of particles of up to approximately 200 mierons for a period of at least about 30 days.

W O 97/12019 PCT~US96/15522 Relation of Zero Shear Viscosity to SusPension - The capability of a detergent composition to suspend insoluble particles is dependent on the composition's zero shear viscosity. This relationship is modeled by Stoke's Law.
v=2(ds-dfl)g.r2/9.~
wherein v is the sedimentation rate of the insoluble; ds is the density of insoluble to be suspended; dfl is the density of fluid to suspend the insoluble, g is gravity; r is radium of the insoluble, rl is viscosity.
According to Stoke's Law, the rate of particle sedimentation is inversely proportional to the viscosity, i.e., the higher the viscosity, the more stable the suspension will be. Thus, a high "zero shear" viscosity is preferred, i.e., for this invention a zero shear viscosity of above about 1 00,000cp, preferably above about 500,000cp, even more preferably above about 1 ,000,000cp is desired.
The rheology and the suspending ability of these compositions are believed to be caused by the formation, in the specific compositions of this invention, of a space filling network of liquid crystalline surfactant particles (also known in the art as liposomes or vesicles) having a typical size of about 0.1 to about 10 microns.
Moreover, the rheological property of the compositions herein is believed to be due in part to the presence in specific amounts of certain electrolytes, including sodium sulfate and citrate. Without being limited by theory, it is believed that the presence of electrolytes acts to control the size of the liquid crystalline surfactant particles.
Thus, the structured nature of the compositions herein are affected by the choice of surfactants and by the amount of electrolytes present. In preferred embodiments herein, the compositions will further comprise from 0% to about 10%, more preferably from about 2% to about 6%, even more preferably from about 3% to about 5%, of a suitable electrolyte or acid equivalent thereof. Sodium citrate is a highly preferred electrolyte for use herein.
The compositions herein contain less than about 10%, preferably less than about 7%, more preferably less than about 5%, by weight of solvents and hyLotr~L)es. Without being limited by theory, it is believed that the presence of solvents and hydrotropes can affect the structured versus isotropic nature of the compositions, compositions cont~ining over about 10% solvents and/or hydrotrope lose the ability to remain in a single "phase", i.e., the composition will appear to separate into two or more layers. By "solvent" is meant the commonly used solvents in the detergent industry, including alkyl monoalcohol, di-, and tri-alcohols, ethylene glycol, propylene glycol, propanediol, ethanediol, glycerine, etc. By "hydrotrope" is meant the commonly used hydlot~opes in the detergent industry, including short chain s-l,r~ that help solubilize other surf~t~nt~ Other wo 97~12019 PCT~US96J15522 examples of hydrotropes include cumene, xylene, or toluene sulfonate, urea, C8 or shorter chain alkyl carboxylates, and C8 or shorter chain alkyl sulfate and ethoxylated ~ f~tes The heavy duty liquid laundry detergent compositions herein contain an anionic surfactant component and a quaternary surfactant as essential ingredients.
Anionic Surfactant Component - The detergent compositions herein comprise from about 10% to about 40%, preferably from about 15% to about 25%, by weight of the d~ g~ composition, of an anionic surfactant component. The anionic surfactant component contains alkyl sulfates and/or alkyl polyethoxylate sulfates, and may contain other non-soap anionic surf~çt~nt~ or mixtures thereof. The anionic surfactant components should not contain more than about 5%, preferably less than about 1%, more preferably substantially free, of fatty acids.
Generally spe~king, anionic surfactants useful herein are disclosed in U.S.
Patent No. 4,285,841, Barrat et al, issued August 25,1981, and in U.S. Patent No3~9l9~678~T~ ghlin et al, issued December 30, 1975, both incorporated herein by reference.
Useful anionic sulra- ~lL. include tne water-soluble salts, pa~ticularly tne alkali metal, ammoniurn and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in theirmolecular structure an alkyl group cont~inin~ from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl"
is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl slllf~tes, especially those obtained by slllf~tin~ the higher alcohols (Cg-Clg carbon atoms) such as those produced by reducing the glycerides of tallow orcoconut oil.
Other anionic sllrf~ct~nt~ herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates co..~ g from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.Other useful anionic sllrf~rt~ntc herein include the water-soluble salts of esters of a-sulfonated fatty acids co-~ from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-solublesalts of 2-acyloxy-alkane-1-sulfonic acids co~ from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety, water-soluble salts of olefin sulfonates cont~inin~ from about 12 to 24 carbon atoms; and ,B-alkyloxy alkane sulfonates cu..l~ from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

W O 97/12019 PCTnUS96/15522 Particularly preferred anionic surfactants herein are the alkyl polyethoxylate sulfates of the formula RO(C2H4O)xsO3 -M
wherein R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated, M is a cation which makes the compound water-soluble, especially an alkali metal, ammoniurn or substituted amrnoniurn cation, and x averages from about 1 to about 15.
Preferred alkyl sulfate surfactants are the non-ethoxylated C12 15 primary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65~F (18.3~C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
The anionic surfactant component of the present compositions comprises from about 5% to about 40%, preferably from about 7% to about 36%, most preferably from about 10% to about 25%, by weight of the detergent composition, of alkyl sulfates or alkyl polyethoxylate sulfates as described above.
Moreover, the anionic surfactant component herein must comprise no more than about 5% of fatty acids. Most preferably, the d~lelgen~ compositions hereineontain no fatty acids. These include saturated and/or unsaturated fatty acids obtained from natural sources or synthetically prepared. Examples of fatty acidsinclude capric, lauric, myristic, palmitic, stearic, arachidic, and behenic acid. Other fatty acids include palmitoleic, oleic, linoleic, linolenic, and ricinoleic acid.
Ql-~tçrn~ry Ammonium Surfactants The compositions herein also contain from about 1% to about 10%, preferably from about 2% to about 7%, more preferably from about 3% to about 5% by weight of a q~ e. ~-;, y ammonium surfactant of the formula:

N X e wherein R1 and R2 are individually selected from the group consisting of C1-C4 alkyl, Cl-C4 hydroxy alkyl, benzyl, and -(C2H4O)XH where x has a value from about 2 to about 5; X is an anion; and (1) R3 and R4 are each a C6-C14 alkyl or (2) R3 is a C6-C 1 8 alkyl, and R4 is selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, benzyl, and -(C2H4O)XH where x has a value from 2 to 5.
Plc:reLled qll~tern~ry ammoniurn surfactants are the chloride, bromide, and methylsulfate salts. Examples of preferred mono-long chain alkyl qu~t.orn~
ammonium surfactants are those wherein R1, R2, and R4 are each methyl and R3 is a Cg-C16 alkyl; or wherein R3 is Cg 18 alkyl and Rl, R2, and R4 are selected from W O 97/12019 PCT~USg6/1552Z

methyl and hydroxyalkyl moieties. Lauryl trimethyl ammonium chloride. myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride. coconut trimethylammonium chloride, coconut trimethylarnrnonium methylsulfate. coconut dimethyl-monohydroxy-ethylammonium chloride, coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy-ethylammonium chloride, steryl dimethyl-monohydroxyethylarnmonium methylcl~lf~te, di- C12-C14 alkyl dimethyl ammonium chloride, and mixtures thereof are particularly preferred. ADOGEN 412TM, a lauryl trimethyl ammonium chloride commercially available from Witco, is also preferred. Even more highly ~ f~llcd are the lauryl ~ elhyl ammonium chloride and myristyl trimethyl ammonium chloride.
Inventions herein comprise the detergent composition wherein the weight ratio of anionic surfactant component to ~ te~n~ry ammonium surfactant is from about 1.5:1 to about 5:1, preferably from about 1.5:1 to about 4.5:1, more preferably from about 2:1 to about 4:1, even more preferably from about 2:1 to about 3.5:1.
O~tional ComPonents The compositions of the present invention can also preferably contain up to about 10%, preferably from 0% to about 5%, more preferably from 0% to about 3%, by weight of an ethoxylated nonionic surfactant. These materials are described in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, incorporated herein by reference. Preferred are the ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4)nOH, wh~ R is selected from the group con.~ tin~ of aliphatic hydrocarbon radicals co..~ from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These s---fact~nte are more fully described in U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981, incorporated herein by reference. Particularly plere.l~d are ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol.
The compositions herein also preferably contain up to about 30%, more preferably from about 1% to about 20%, most preferably from about 1% to about 10%, by weight of a non-citrate, non-fatty acid detergent builder material. While all manner of detergent builders known in the art can be used in the present compositions, the type and level of builder should be selected such that the final composition has an initial pH of from about 6.0 to about 11.0, preferably from about 7.0 to about 9.0, at a con~ t-~tion of about 10% by weight in water at 20~C.

W O 97/12019 PCTrUS96/15522 Detergent builders are described in U.S. Patent No. 4,321,165, Smith et al, issued March 23, 1982, incorporated herein by reference. Preferred builders for use in liquid d~L~ ,gent~ herein are described in U.S. Patent No. 4,284,532, Leikhim et al, issued August 18, 1981, incorporated herein by reference.
Enzvmes Enzymes can be included in the forrnulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, lipases, and cellulases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus activedetergents, builders and so on. In this respect bacterial or fungal enzymes are .ler~ d, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufficient to provide up to about S mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme pergram of the composition. Stated other~vise, the compositions herein will typically eomprise from about 0.001% to about 5%, preferably 0.01% to 1% by weight of a comrnercial erlzyme p~ lion. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH
range of 8-12, developed and sold by Novo Industries A/S under the registered tr~(len~rne ESPERASE. The pl~dlion of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic erl7ymes suitable for removing protein-based stains that are comrnercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denrnark) and MAXATASE by International Bio-Synthetics, Inc.
(Ihe Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
Amylases include, for exarnple, a-arnylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, Tntern~tional Bio-Synthetics, Inc.and TERMAMYL, Novo Tn-ln~tries CA 02233474 l998-03-30 W O 97~12019 PCT~US96/15522 The cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247 832. CAREZYME (Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced by microorg~ni~m~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available *om Toyo Jozo Co., Tagata, Japan; and filr~her Chromobacter viscosum lipases from U.S. Biochemic~l Corp., U.S.A. and Diosynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola l~nllginosa and commercially available from Novo (see also EPO 341,947) is a plefe.l~,d lipase for use herein.
A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in deLel~ ~:llL~, can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.The enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or m~gne~ium ions in the fini~h~cl compositions which provide such ions to the enzymes. ~Calcium ions are generally somewhat W O 97/12019 PCTAUS96tlS522 more effective than m~gn~sium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species. See Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from about 1 toabout 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calciurn ion per liter of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions. The level of calcium or m~gnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition. Any water-soluble calcium or m~gne~ium salt can be used as the source of calciurn or m:~gnesiurn ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate~ calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding m~gne~ium salts. A small amount of calciurn ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calciurn in the enzyme slurry and forrnula water. In solid detergent compositions the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or m~gnçsium ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of greaseremoval perform~n~e. Accordingly, as a general proposition the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calciurn or m~gne~ m ions, or both. The amount can vary, of course, with the amount and type of enzyme employed in the composition.
The compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is ~,efelled, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodiurn pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid.

W O 97112019 PCT~US96~22 Other preferred components for use in liquid detergents herein are the neutralizing agents, buffering agents, phase regulants, polyacids, suds regulants, opacifiers, dispersants, such as ethoxylated tetraethylene pentzl~mine, antioxidants, bactericides, dyes, soil release polymers, perfumes, and brighteners described in the U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981, incorporated herein by reference. Preferred neutralizing agents for use herein are organic bases, especially triethanolamine and monoethanol amine~ which results in better detergency performance than inorganic bases such as sodium and potassium hydroxides.
The compositions herein are suitable for suspending insoluble particles.
Particles for suspension include alkyl amine-anionic surfactant ion pair particles, as disclosed in U.S. pat. no. 4,861,502; builders such as zeolites; bleach particles;
perfume particles; encapsulated detergent additives; and other known insouble laundry additives.
The following non-limitin~ examples illustrate the compositions of the present invention. All percentages, parts and ratios used herein are by weight unless otherwise specified.
- EXAMPLE I-IV
Liquid detergent compositions were p,e~ued according to the following formulas.
In~redients Example I Examples II
C12-15AE2.5SH 16 16 C45EO7 2.0 0 C12TMAC 5.0 5.0 Citric acid 5.0 5.0 NaOH ~4.5 ~4.5 H20 balance balance pH 7.0-8 7.0-8 Appea~ ce Opaque Opaque Suspension Suspension Zero ShearViscosity 2.5 8.2 l o6cp Viscosity (20/s) cp 300 2000 In~redients ExamPle III Examples IV
C12-15AE2.5SH 16 10 C45EO7 2.0 0 C 12TMAC 3.0 5.0 W O 97/12019 PCT~US96/15522 Citricacid 5.0 4.0 NaOH ~4.5 ~.0 H20 balance balance pH 7.0-8 7.0-8 Appearance Phase Suspension Separation Zero Shear Viscosity --- 0.68 1 o6cp Viscosity (20/s) cp --- 400 The detergent sarnples are made by the following procedure.
Anionic surfactant paste, C 12-15 alkyl ethoxylate sulfate, is first mixed with alkyl ethoxylate, C 14-1 sEO7 (if present) according to the formula composition,which is followed by the addition of of sodium hydroxide. Citric acid is added immediately after NaOH to bring the pH to about 7.0-8.0 at 10% solution. Lauryl trimethyl ammonium chloride is then added. Immediately after the addition of lauryl trimethyl arnmonium chloride, an opaque, lamellar droplet-filled suspension sarnple is formed. Water and other ingredients are added at the end to complete the formulation.
The compositions of Example I, II, and IV have a viscosity/rheology capable of suspending solids and are stable for more than 30 days.
The composition of Example III undergoes phase split and is undesirable in commercial products.

EXAMPLES V-XT
Liquid detergent compositions were prt;p~.,d according to the followin - forrnulas.
Samples V VI VII VIII IX X XI
C25AE2.5S -- 20 -- 13.3 -- 20 --C45AE2.25 S -- -- 13 -- 16 -- 20 C 1 2TMAC 5 5 4. l 4.2 -- 4 4 C14TMAC -- -- -- -- 5.0 -- --C45EO7 2 0 1.6 1.6 2.0 0 0 Citric Acid 5 5 6.0 4.2 5.0 2.0 0.5 Borax 1.5 0 1.6 0 2.0 0 0 Propylene 6.4 4.7 3.8 3.7 4.6 4.7 4.7 glycol Ethanol 0 2.2 1.5 1.8 2.3 2.2 2.8 NaOH to pH 7-9 Water to 100%

CA 02233474 l998-03-30 W V 9~1~20~9 PCT~US96J15522 Zero Shear 5.68 0.7 9.9 13 110 -- n/a Viscosity 106 Cp Anionic/Cationi 3/1 4/1 3/1 3/1 3/1 5/1 5/
c Ratio Viscosity* cp 3000 2400 1700 1440 3300 split 1800 ~, *Viscosity is measure at 20s~l.
C25AE2.5S is C12 15 alkyl ethoxylated sulfate with an average degree of ethoxylation of 2.5. C25AS is C12 15 alkyl sulfate. C45AE2.25S is C14 15 alkyl ethoxylated sulfate with an average degree of ethoxylation of 2.25. C 12TMAC is C 12 trimethyl ammonium chloride. C 14TMAC is C 14 trimethyl ammonium chloride. C45EO7 is C14 15 alcohol ethoxylate with an average degree of ethoxylation of about 7.
The compositions of Example V-IX and XI have a viscosity/rheology capable of suspending solids and are stable for more than 30 days.
Example X with an anionic/cationic surfactant ratio of 5: 1 forrns a split phase.
However, with routine adjl-~tment of the level of electrolyte and of the chain length of the anionic surfactant, a composition of Exarnple XI with the same anionic/cationic ratio is structured and more phase stable.
EXAMPLE XII
Liquid d~lelg~,lt compositions were prepared according to the following forrnulas.
Component A B C
Sodium C12-15 alkyl 20.0 15.0 25.0 polyethoxylate (2.5) sulfate Lauryl trimethyl ammonium 5.0 5.0 5.0 chloride C12 13alkylpolyethoxylate(9) 2.0 2.0 2.0 Cl2 alkyl glucose amide 5.0 5.0 5.0 Citric acid 3.0 3.0 3.0 C12 14 alkyl fatty acid 2.0 2.0 --Ethanol 3.7 3.7 3.7 Propanediol 8.0 8.0 8.0 Monoethanolamine I .1 l . l 1.1 Boric acid 3.5 3.s 3.5 Tetraethylenepe~ l l i "~ 1.2 1.2 1.2 ethoxylated (15-18) Sodium cumene sulfonate 3.0 3.0 3.0 W O 97/12019 PCT~US96/15522 Protease enzyme 0.9 0.9 0.9 Lipase enzyme 0.1 0.1 0.1 Cellulase enzyme 0.08 --- 0.08 Sodium hydroxide to pH = 8 Water, per~me and minor to balance 100%
ingredients anionic/cationic surfactantratio 4/1 ¦ 3/1 ¦ 5/1 While the compositions of Example XII have anionic/cationic ratios within the specified ranges of this invention, they are nonetheless outside the scope of this invention because they are isotropic due to the presence of > 10% solvents and hydrotropes. The compositions of Example XII does not have a viscosity/rheology capable of suspending solids.

Claims

1. A structured, heavy duty liquid laundry detergent composition comprising, by weight of the composition:
a) from 10% to 40% of an anionic surfactant component which comprises, by weight of the composition:
(i) from 5% to 40% of alkyl sulfates or alkyl polyethoxylate sulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the polyethoxylate chain contains from 0 to 15 ethylene oxide moieties; and (ii) no more than 5% of fatty acid surfactants; and b) from 1% to 10% of a quaternary ammonium surfactant having the formula wherein R1 and R2 are individually selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4O)XH where x has a value from 2 to 5; X is an anion; and (1) R3 and R4 are each a C6-C14 alkyl or (2) R3 is a C6-C18 alkyl, and R4 is selected from the group consisting of C1-C10 alkyl, C1-C10 hydroxy alkyl, benzyl, and -(C2H4O)XH where x has a value from 2 to 5;
c) no more than 10%, by weight, of solvents or hydrotropes; and d) from 0% to 10% of a suitable electrolyte or acid equivalent thereof;
provided that the weight ratio of anionic surfactant to quaternary ammonium surfactant is from 1.5:1 to 5:1; and wherein said anionic and quaternary ammonium surfactants form liquid crystalline particles.

2. The composition of Claim 1 wherein said composition has a viscosity at 20s-1 shear rate of from 100 cp to 4,000 cp, preferably from 100 cp to 2,000 cp.

3. The composition of Claim 1 wherein said composition has a zero shear viscosity above 500,000cp.

4. The composition of Claim 1 comprising from 15% to 25% of the anionic surfactant component and less than 7%, by weight of solvents or hydrotropes.

5. The composition of Claim 4 wherein the anionic surfactant component of the anionic surfactant comprises from 7% to 36%, preferably from 10% to 25%, alkyl ethoxylated sulfates.

6. The composition of Claim 5 comprising from 3% to 5% of the quaternary ammonium surfactant.

7. The composition of Claim 1 wherein the quaternary ammonium fabric-softening agent is selected from the group consisting of lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, coconut trimethyl ammonium chloride, coconut trimethyl ammonium methylsulfate, coconut dimethyl-mono-hydroxyethylammonium chloride, coconut dimethyl-monohydroxy-ethylammonium methylsulfate, steryl dimethyl-monohydroxyethyl-ammonium chloride, steryl dimethyl-monohydroxyethylammonium methylsulfate, di-C12-C14 alkyl dimethyl ammonium chloride, and mixtures thereof.

8. The composition of Claim 7 comprising from 3% to 5% of lauryl trimethyl ammonium chloride.

9. The composition of Claim 7 comprising from 3% to 5% of myristyl trimethyl ammonium chloride.

10. The composition of Claim 1 wherein the weight ratio of anionic surfactant component to quaternary ammonium surfactant is from 2:1 to 3.5:1.

11. The composition of Claim 1 further comprising up to 10% of an ethoxylated nonionic surfactant.

12. The composition of Claim 1 further comprising from 1% to 20% of a non-citrate, non-fatty acid detergent builder material

13. The composition of Claim 1 further comprising an enzyme selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof at a level sufficient to provide from 0.01 mg to 3 mg of active enzyme per gram of the composition.

14. The composition of Claim 1 wherein said composition is capable of suspending particles of up to approximately 200 microns for a period of at least one month.