GB2355015A - Structured liquid detergents with selected perfume fragrance materials - Google Patents

Abstract

Heavy duty gel or liquid laundry detergent compositions comprise, an anionic surfactant, a perfume composition and a structurant; the perfume composition includes specially selected hydrophobic fragrance materials which can be incorporated into a lamellar phase in the detergent composition thus suppressing the overall odor intensity of the detergent composition. Other components of the composition include citric acid, enzymes, brighteners, ethanol, monoethanolamine, caustic soda, borax, suds suppressor and a dye.

Description

7695 2355015 STRUCTURED LXQMD DETERGENTS WITH SELECTED PERFUME FRAGRANCE

MATZRIALIS FULD OF _Tffg DWENTION

This invention relates to structured liquid or gel laundry detergent products comprising an anionic surfactant, a structurant and specially selected hydrophobic, low volatility perfumes. BACKGROUND OF THE INVTNTION

Liquid laundry detergent products offer a number of advantages over dry, powdered or particulate laundry detergent products. Liquid laundry detergent products are readily measurable, speedily dissolved in wash water, non-dusting, are capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and usually occupy less storage space than granular products. Additionally, liquid laundry detergents may have incorporated into their formulations materials which would deteriorate in the drying operations employed in the manufacture of particulate or granular laundry detergent products. Because liquid laundry detergents are usually considered to be more convenient to use than granular laundry detergents, they have found substantial favor with consumers.

However, the formulation of liquid laundry detergent compositions also presents difficulties, particularly in regard to incorporating perfumes into the detergent compositions. Perfumes are formulations of one or more constituent fragrance materials, A formulator of perfume compositions selects these fragrance materials so that the overall perfume composition has a scent that conveys fresImess and cleanliness to a consumer when the scent is deposited on a garment or otber textile article. Because the most immediate perception that a consumer has of the effectiveness of a laundry detergent composition is the scent that the detergent composition has imparted to textile articles, it is extremely important that the detergent composition deliver sufficient, enduring perfume composition to the surface of textile articles to provide a perceptible signal to a consumer that the detergent compositions have provided substantial cleaning and refreshing benefits. it is equally important that when this perfume is delivered to the surface of a textile article, it is retained througli both subsequent washing and drying processes.

There are at least two reasons why perfumes included in a detergent composition may nonetheless not provide freshening benefits to a textile article after successive washing and drying processes. First, during an aqueous wash process (such as in a domestic clothes washr-T) the perfumes may be absorbed into the aqueous laundry detergent solution rather than being imparted to the surface of the textile ardcle. A second reason is that perfumes may be degraded 7695 and evaporated in a heated environment, such as a domestic clothes drycr. Thus it is often necessary to incoiporate relatively high levels of perfume into a detergent composition in order to insure that a satisfactory amount of perfume is delivered to the surface of the textile article and then retained on the surface through subsequent washing and drying processes. But these high levels of perfume in a detergent composition can be difficult to stabilize and may give the liquid detergent composition a-pungent, strong odor that many consumers dislike.

One alternative to using high, malodor-causing levels of perfume composition is to include in the perfume composition certain hydrophobic fragrance materials which are especially likely to be retained on the surface of a garment or textile article during washing and drying. Because these fragrance materials are hydrophobic, they arc more likely to cling to a hydrophobic surface like the surfacc of a textile article, and less likely to be absorbed into the aqueous laundry detergent solution. However, even when included at lower concentrations, hydrophobic materials may still contribute to the pungent, strong odor to which most consumers arc adverse.

Thus there is a continuing need for laundry detergent compositions which can deliver to the surface of a textile article perfumes which are likely to be retained through both subsequent washing and drying of the textile article. Accordingly a benefit of the present invention is that a liquid laundry detergent composition is provided which contains a perfume component that imparts a pleasing and enduring scent to textile and garment articles during a washing process but the detergent composition lacks the strong, pungent perfume odor that is undesirable to consumers.

Nearly all liquid detergent compositions can be classified as being either "structured" or isotropic liquids. Isotropic liquids are homogeneous, all of the ingredients having been dissolved into the solvent. By contrast in an intemally structured liquid, while some of the ingredients may have been dissolved in the solvent, there arc also ordered liquid crystal structures. Without being lirnited by theory, it is believed that the shape of the liquid crystal is detcnnined by the preferred geometric packing arrangement, In the case of arnphiphiles such as ionic surfactants, the packing arrangement is strongly influenced by the size of the hydropl-dlic polar head group and the strength in the liquid mixture of electrostatic forces which attract or repel the polar head group. c teri al o er In addition to providing a pleasing fragrant scent hydrophobic frag= c ma als SO ff another important benefit: because of their hydrophobicity it is possible incorporate the fragrance materials into an internally structured liquid detergent thereby lowering the overall odor intensity that the perfume contributes to the detergent composition.

2 7695 Thus without intending to be limited by theory, it is believed that fragrance materials can be incorporated into the highly hydrophobic areas of the lamellar liquid crystals which are contained in the structured liquid detergent composition thereby suppressing the odor intensity of the fragrance materials and thus reducing the odor intensity of the detergent composition. When the detergent composition is then dissolved in water to form a detersive aqueous solution, the larnellar phase melts and the fragrance materials are released into the aqueous solution where they are subsequently deposited on the surface of a textile article.

SUNIMARY OF THE DWETMON It has now been determined that when certain hydropbobic fragrance materials we incorporated into a structured liquid laundry detergent composition, such detergent compositions will impart a durable scent to the textile articles washed in the detergeni compositions without giving the detergent compositions themselves an unpleasant odor which is adverse to consumers. it is thus a benefit of the present invention ftt an internally structured liquid or gel laundry detergent composition is provided which has excellent cleaning performance, acceptable product rheology and imparts a pleasing and enduring scent to a textile article.

in a first aspect, the present invention encompasses a heavy duty liquid or gel laundry detergent compositions comprising, by weight of the composition:

a) from about 10% to about 40% of an anionic surfactant; b) a perfume composition, wherein at least about I% of the perfume composition conVrises fragrance materials selected from the group consisting of fragrance materials having a logP of at least about I C) a structurant.

In a second aspect, the present invention encompasscs a heavy duty liquid or gel laundry detergent compositions which is either wholly or partly in lamellar forinand comprises a) from about 10% to about 40% of an anionic surfactant, b) from about 0. 1 1/a to about 3.0%of a perfume composition, wherein at least about I % of the perfume composition comprises fragrance materials selected from the group consisting of fragrance materials having a logP of at least about 3.

c) at least 0.5 % of a structurant; d) an arninc selected from the group consisting of detersive an-Anes, modified polyarnines, polyatnide-polyanlines, polyetboxylated-polymnine polymer$, quaternary ammonium surfkctants and mixtures thereof, 3 1 7695 wherein the viscosity of the detergent composition is from about 100 cps to about 4,000 cps when measured at a temperature of 25T and at a shear rate of.20 s All pans, percentages and ratios used herein are expTessed as percent weight unless otherwise specified. All temperatures are in degrees Celsius (0 C) unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.

DETAILED DESCRIPTION OF THE MENTION

As used herein, Iog?' includes loj]? values determined by observation or experimentation and those values obtained through calculation by the use of the CLOGP program.

By "transparent" it is meant that light is easily transmitted through the gel detergent compositions of the present invention and that objects an one side of the gel composition are at least partially visible from the other side of the composition.

The present invention includes a perfume composition selected to providc a fresh sensory impression on the surface of a textile article to which the perfume composition is imparted. The perfume composition is typically present at a level of from about 0.05 % to about 3.0 %, preferably from about 0 A % to about 2 %, most preferably from about 0.2 % to about I %, by weight of the detergent composition- The perfume compositions are themselves comprised of fragrance material. It is an essential part of the present invention that some of these fragrance materials be hydrophobic. The degree of hydrophobicity of a fi- agrance material can be correlated with its octanol/water partitioning cocfficient (-P"). lie octanol/water partition coefficient of a fragrance material is the ratio between its equilibrium concentration in octanol and in water. A fragrance material with a greater partition coefficient P is more hydrophobic. Conversely, a fragrance material with a smaller partition coefficient P is more hydrophilic. In the present invention, hydrophobic fragrance materials are those with an octanollwater partition coefficient P of 1000 or greater. Since the partition coefficient of the fragrarice materials normally have high value, they are more conveniently given in the form of their logaritbin to the base 10, log P. Preferably, al least about I %, more preferably at least about 3 %, most preferably at least about 5 %, by weigbt, of the perfume composition is composed of fi-agrance materials which have logp values of at least 3. The composition will also preferably contain no more than about 95 %, more preferably no more than about 90 %, most preferably no more than about 80 % of fragrancc materials which have JogP values of at least I 4 7695 The legl? of many perfume ingredients has been reported; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylog CIS), Irvine, Calif, contains many, along with citations to the original literature. However, the loSP values are most conveniently calculated by the "CLOGP" prograinalso available from Daylight CIS. This program also lists expedmental loSP values when they are available in the Pornona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf. A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by refemce), The fragment approach is based on the chemical structure of each perfume ingredient, and takes into account the numbers and types of atoms, the atom cormectivity, and chemical bonding. The ClogP values, which are the most reliable and widely used estiniates for this physicochm-nical property, are used instead of the experimental log]? values in the selection of perfume ingredients which are usefW in the present invention.

Nonlimiting examples of suitable fragrance materials and their respective ClogP values include the following:

ce Material Q O Alpba-Hexylcinnamaldehyde 4.9 Alpha-Methylionone 4.5 Ambretone 6.0 CeWoX 5.0 Cis-3-Hexenyl Salicylate 4.6 Citronellat 3.3 Cyclamen Aldehyde 3.5 Cyclohexyl Salicylate 4.5 Dlydro Linalool 3.0 Dihydromyrcenol, Dimethyl Benzyl Carbinyl Acetate 3.1 Ganuna-Dodecalactone 4.0 Gamma-Undecalactone 3.4 Geranyl Nitrile 3.3 Isobornyl Acetate 3.5 Lilial 4.1 N-Hexyl Salicylate 5.1 Nerol 3.1 Norlimbanol 5.9 Pentadccanolide 5.7 Phenethyl Phenylacetate 4-0 Polysantol 5.0 Rhodinol 3.3 Terpineol (AlphaBetaGamma) 3.1 Tetrahydrolinalool 3.5 Tonalid 6.3 Trifone 4.0 TO further increase the durability of the scents deposited on textile and garment articles, it may also be desirable to include fragrance n- mterials in the perfume composition which are not only hydrophobic but are also of a low-volatility, meaning that they have a boiling point of at least 250T. Because of their higher boiling points, these fragrance materials are less likely to be evaporated in a clothes dryer. If it is desired to use a fragrance material that is not only hydrophobic but of low-volatility then preferably, at least about I %, more preferably at least about 3 %, most preferably at least about 5 %, by weight, of the perf-Lime composition is composed of fragrance materials which have lagP values of at least 3 and boiling points of 250C or greater. The composition will also preferably contain no more than about 90 %, more preferably no more than about 65 %, most preferably no more Omn about 55 % of fragrance materials which have I ogP valucs of at least 3 and boilinj points of 250C or greater.

Nonlirniting examples of suitable fragrance materials and their respective boiling points include the following:

FT#Z=ce Material Boiling Point (_Q Alpha-Metbylionone 291 Arnbretone 338 Cetalox 280 Cis-3-Hexenyl Salicylate 316 Cyclamen Aldehyde 274 Cyclohexyl Salicylate 325 Gamma-Dodecalactone 288 6 7695 Gamma-Undecalactone 260 Lilial 287 N-Hexyl Salicylate 311 Norlimbanol 297 Pentadecanolide 329 Phenethyl Phenylacetate 350 Poly.rAmtol 297 Tonalid 344 Trifone 444 Structurants - Tle detergent compositions herein contain at least 0.5 %, preferably at least 1.0%, more prefcrably at least 2.0% of a structurant. The selection and concentration of structurants is important because the particular combination of structurants and surfactants will determine whether the liquid detergent composition will be a structured liquid or an isotropic liquid.

Additionally, the combination and concentration of surfactants and structurants will also determine the viscosity of the detergent The rheology bebavior can be modeled by the following f0mula.

11 TIO + KY(n-1) wberc: il is the viscosity of the liquid at a given shear rate, -qo is the viscosity at infinite Shear rate, y is the shear Tate, n is the shear rate index, and K is the consistency. Structured liquid detergents arc known to have an infinite shear viscosity (ijo) value between 0 and about 3,000op (centipoise), a shcar index (n) value of less than about 0.6, a consistency value, K, of above about 1,000, and a viscosity (YI) measured at 20-1 of less than about 10,000cp, preferably less than about 5,000cp. Under low stress levels, a "zero shear" viscosity is above about 100,000cp wherein "zero shear" is meant a shear rate of 0.00 1 a- I or less. The yield value of the compositions herein, obtained by plotting viscosity versus stress, is larger than 0.2Pa. These rbeology parameters can be measured with any commercially available rheometer, sucb as the Canimed CSL 100 model. The particular compositions of the present invention havc a viscosity at 20 s-I shear rate of frorn about 100 cps to about 4,000 cps, preferably from about 300 cps to about 3,000 cps, more preferably from about 500 cps to about 2,000 cps and are stable upon storage.

7 7695 Materials which can perfonn the role of a structurant include electrolytes and builders. When included herein, these materials function not only as structurants but also perform in their conventional roles in a detergent composition.

Suitable for use herein are those electrolytes known as "salting-out" e1cctrolytes. These include water-soluble builder salts, such as the alkali metal ortho- and pyrophosphates, the alkali metal tripolyphosphates, the alkali metal silicates, borates, carbonates, sulfates, alkali metal citrates, alkali metal salts of nitrilotriacetate, alkali metal salts of carboxymethyloxy succinatc. Arrimoniurn salts of the above anions may be used instead of alkali salts.

Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces, as wcII as to provide benefits as an electrolyte. Builder level can vary widely depending upon end use and physical form of the composition. Built detergents typically comprise at least about 1% builder. Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder. Lower or higher levels of builders are not excluded. For example, certain detergent additive or highsurfactant formulations can be unbuilt, Because they also function well as electrolytes, citrates are the most preferred.

Suitable builders herein ran be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those baving chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonatcs and carbonate minerals other than sodium carbonate or sesquicarbonate; alurninosilicates; organic rnono-, di, tri-, and tetracarboxylates cspecially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt forni, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.

Builder mixtures, sometimes termed "builder systems" can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately wben describing quantities of materials herein.

Phosphorus containing dctergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolainmonium salts of 9 7695 polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric metaphosphates; and phosphonates.

Suitable silicate buildcrs include alkali mctal silicates, particularly those liquids and solids having a SiO2:Na2O ratio -in the range 1.6-1 to 3.2: 1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under the trade name BRlTESIL(&, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. F. Rieck, See preparative methods in German DE-A-3,417,649 and DE-A3,742,043.

Also suitable for use herein are synthesized crystalline]on exchange materials or hydrates thereof as taught in U.S. 5,427,711, Sakaguchi et at, June 27, 1995, Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,32 1,001 published on November 15, 1973.

Alurninosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids. Suitable for the present purposes are those having empirical forriuila: [Mz(AI02)z(SiO2)vl- XH20 wherein z and v are integers of at least 6, the molar ratio of z to v is in the Tange from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates, can be crystalline or amorphous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3, 985,669, Krummel, et al, October 12, 1976. Preferred synthetic crystalline aluniinosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP.

Suitable organic detcrgcnt buildm include polycarboxylatc compounds, including watersoluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lifturn, or alkanolammonium salts are preferred. Polycarboxylate builders 'include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128, 287, April 7, 1964, and Larnberd et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S. 4,663,07 1, Bush et al, May 5, 1987; andother ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120, 874 and 4,102,903.

other suitable buildcrs are the ether hydroXypolycaTboxylates, copolymers of maleic anhydride witb ethylene or vinyl methyl ether; 1, 3, 5trihydroxy benzene-2, 4, 6-trisulpbonic acid; carboxymethyloxysuceinic acid; the various alkali metal, ammonium and substituted 9 7695 ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mcllitic acid, succinic acid, pol)nnaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Oxydisuccinates are also especially useful in such compositions and combinations.

Certain detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants. Ptefwed types for builder ftrrictionality are illustrated by: 3,3-dicarboxy4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.

7 lky a alk n 1 4,566,984, Bush, January 28, 1986. Succinic acid builders include the C5- C.0 2 1 nd e y succinic acids and salts thereof. Succinate builders also include: lauryisuccinatc, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl-succinates are described in European Patent Application 86200690. 5/0,200,263, published November 5, 1986. Fatty acids, e.g., C I 2-C 18 monocarboxylic acids, can also be incorporated into the compositions as smfactant(builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable polycarboxylates, are disclosed in U.S. 4,144,226, Crutchfield ct al, March 13,1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322. c)- Lolven.t By "solverif '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. d) Hydrotr

Mes By "hydrotrope"' is meant the commonly used hydrotropes, in the detergent industry, including sbort chain surfactants that help solubilize other surfactants such as aromatic sulphonates. Other examples of hydrotropes include cumene, xylene, or toluene sulfonate, urm, C8 or shorter chain alkyl carboxylates, and Cg or shorter chain alkyj sulfate and ethoxylated sulfates.

The compositions herein may optionally contain from about 0% to about 10%, by weight, of solvents and hydrotropes.

e) Aminocarboxylate Chelating Agents The present detergent compositions may contain aminocarboxyIate sequestrants, which without intending to be bound by theory, are believed to provide benefits to detergent 7695 compositions because their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates. They can also function as structurants. Arninocarboxylates suitable for use in the present invention comprise one of the following arnines:

-N-CH2(CH2COOFT)(COONI), and - N(MOOCCH2)2, M is selected from the group consisting of hydrogen, an alkali metal, arnmonium and mixtures thereof Suitable aminocarboxylatc squestrants include ethylencdiaminetetracetates, Nhydroxycthylcthylenedianiinctriacetates, nitrilotriacetates, etbylenedismine tetraproprionates, triethylenctetraaminchexacetates, diethylenetliaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

0 Other Chelating Ag-ents Besides aminocarboxylates, the present detergent compositions may also include other chelating agents such as Amino phosphonatcs are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. It is preferred that those amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms. A preferred biodegra&blc chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the LS,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

Modified Rol)%mine - The compositions herein may comprise at least about 0.05%, preferably from about 0.05% to about 3%, by weight of a watersoluble or dispersible, modified polyamine agcnt said agent comprising a polyandne backbone corresponding to the formula- (R2)2-N1w-[R3--X3,-[RIjy-jR1-NIZ 2 (A2)2 wherein each RI is independently C2-CS alkylene, alkenylene or arylene; each R2 is independently H. or a moiety of formula OH[(CH2)XO]n, wherein x is from about I to about 8 and n is from about 10 to about 50; w is 0 or 1; x+y+z is from about 5 to about 30; and B represents a continuation of this structure by branching; and wherein said polyarnine before alkylation has an average molecular weight of from about 300 to about 1, 200.

In preferred embodimcrits, RI is C2-C4 alkylene, more preferably ethylene; R2 is OHICH2CH201n, wherein n is from about 15 to about 30, more preferably n is about 20. The average Molecular Weight of the polyamine before alkylation is from about 300 to about 1200, 769S more preferably from about 500 to about 900, still more preferably from about 600 to about 700, even more preferably from about 600 to about 650.

Polyamide-Polyarnine!'; - The gel compositions of the pTesent invention preferably comprisc from about 0. 1 % to 8% by the weight of the composition of certain polyarmdepolyamines, Marc preferably, such polyamide-polyarnine materials will comprise from about 0.5% to 4% by weight of the compositions herein, Most preferably, these polyan-ddepolyamines will comprise frorn about 1% to 3% by weight of the composition.

The polyamide-polyarnine materials used in this invention arc those which have repeating, substituted ainido-amine units which correspond to the general Structural Formula No. I as follows:

0 R3 11 V I -i.

1<4 Structural Formula No. I In StructuTal Formula No. 1, Rl, R2 and R5 are each independently C 1 -4 alkylene, C 1-4 alkarylene or arylene. It is also possible to eliminate Rl entirely so ftt the polyamidepolyamine is derived from oxalic acid.

Also in Structural Formula No. 1, R3 is H, epichlorohydrin, an azetidinium group, an epoxypropyl group or a dimethylan-inohydroxypropyl group, and R4 can be I-I, C 1 -4 alkyl, C 1 -4 alkaryl,oraryl. R4 may also be any of the foregoing groups condensed witb Cl-4 alkylene oxide.

RI is preferably butylene, and R2 and R5 are preferably ethylene. R3 is prefmbly epichlorohydrin. R4 is preferably H.

The polyamide-polyamine materials useful herein can be prepared by rcacting polyamines such as diethylenetriarnine, triethylenetctramine, tetraethylenepentamine or dipropylenetrianiine with C2-C12 dicarboxylic acids such as oxalic, succinic, glutaric, adipic and diglycolic acids. Such materials may then be finther derivatized by reaction with, for example, epichlorohydrin. Preparation of such materials is described in greater detail in Keirn, U.S. Patent 2,296,116, Issued February 23, 1960;Kcim, U.S. Fatent 2,296,154, issued February 23, 1960 and Keim, U-S. Patent 3,332,90 1, Issued July 25, 1967.

The polyarnide-polyaniine agents preferred for use herein are commcrcially marketed by Hercules, Inc. under the trade narne Kyrnene@. Especially useful are KYmene 557HO and 12 7695 Kymenc 55?LXO which are epichlorohydrin adducts of polyamide-polyamines which are the reaction products of dicthylenctriarrdne and adipic acid. Other suitable materials are those marketcd by Hercules under the trade names Retenl- and Delsette6, and by Sandoz under the trade name CartaretinO, These polyamide-polyaminc materials are marketed in the form of agucous suspensions of the polymeric material containing, for example, about 12.5% by weight of solids.

Detergive Arnine - Suitable arnine surfactants for use herein includc detersive amines, according to the formula:

13 Ri-X-(CH2)7r-N I P-4 whervin Rl is a C6-C 12 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or 0 or X can be absent; and R3 and R4 are individually selected from 11, C I -C4 alkyl, or (CH2-M2-0(R5)) wherein R5 is H or methyl.

Prcfcrred amines include tho following Rl-(CH2)2-NH2 RI-O-(CH2)3-NH2 RI-C(O)-NH-(CH2)3-N(CH3)2 1 42-CHM-Rs RI-N JH2-CR(0R)-R5 wherein RI is a C6-C12 alk yl group and RS is H or CH3.

In a highly preferred embodiment, the amine is described by the formula: RI-C(O)-NH-(CH2)3-N(CH3)2 wherein RI is C8-C 12 alkYl - Particularly preferred amines include those selected from the group consisting of octy) amine. hexyl amine, decyl amine, dodcoyl atnine, Cg- Cl 2 bis(hydroxYethYI)amine, C8-C 12 bis(hydroxyisopropyI)arnine, and C8- CI2 amido-propyl dimethYl amine. and mixttres.

if utilized the detersive amines comprise from about 0-1% to about 10%, preferably from about o.5% to about 5%, by weight of the compositionQuaternM Ammonium Surfactants - from about 1% to about 6% of a quaternary a=nontum surfactant baving: the formula 13 769$ R4 R1 R3 R2 wherein R I and R2 are individually selected from the group consisting of C I -C4 alkyl, C I -C4 hydroxy alkyl, benzyl, and -(C2H40)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-C 14 alkyl or (2) R3 is R C6-C 18 21kyl, and R4 is selected from the group consisting of C I -C 10 alkyl, Cl -C 1 o hydroxy alkyl, benzy], and -(C2H40)xH where x has a value ftom 2 to 5; Preferred quaternary ammonium surfactants are the chloride, bromide, and melhylsulfate salts. Examples of preferred mono-long chain alkyl quatemary ammonium surfactants are those wherein Ri, R2, and R4 are each methyl and R3 is a CS-Cl 6 alkyl; oT wherein R3 is CE-1 8 alkyl and RI, R2, and R4 are selected from methyl and hydroxy-alkyl moicties. Lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride, palwityl trimethyl arnmonium chloride, coconut trimcthylammonium chloride, coconut trimethylan=oniurn mothylsulfate, coconut dimethyl-- rnonchydroxyethyl-anunonium chloride, coconut dirnethylmonchydroxyethylammonium methylsulfite, steryl dimcthylmonohydroxy-.ethylammonium chloride, stery) climethylmonohydroxyethylammoniumrnethylsulfate, di- C12-CI4 alkyl dimethyl ammonium chloride, and mixtures thereof are particularly preferred. ADOGEN 412"A, a lauryl trimethyl ammonium chloride conunercially available from Witco, is also preferred. Even more highly preferred are the lauryl trimethyl anunonium chloride and myristyl trimethyl ammonium chloride.

Alkoxylated and otlier quaternary amraonium. surfactants which are suitable for use in the present invention are disclosed in detail in the copending patent application of Eugene S. Sadlows1d, entitled "Aqueous, Gel, Laundry Detergent Composition!', having P&G Case No. 6955, filed under the Patcni Cooperation Treaty, Application No. PCT/TJS98/24809 and international priority date November 26, 1997, which is hereby incorporated by reference.

Pg1wffiglylated-Polyarnine PolMers - Another polymer dispersant form use herein includes polyethoxyated-polyamine polymers (PPP). lie preferred polyethoxylated-polyamines useful herein arc generally polyalkyleneamincs (PAA's), polyalkylencimines (PAXs), preferably polyethylencamine (PEA!s), polyethyleneirrAnes (PEI's). A common polyaftlenearnine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia. and ethylene dichloride, followed by ftactional distillation, The common PEA's obtained are 14 7695 triethYlenetetrarnine (TETA) and teraethylenepentaniine (TEPA). Above the pcntarnines, i.e., the hexamines, heptamines, octamines and possilbly nonamines, the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can aho be present cyclic arnines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1937, which describes the preparation of PERs.

Polyethoxylated polyarnines can be prepared, for example, by polyIncri2ing ethyleneimine in the presence -of a caWyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esse.1mann ct al., issued July 16,1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2, 553,696, Wilson, issued May 21, 1951 Preferred polyethoxyaled-polyarnine polymers useful for this invention aTe alkoxylated quaternary diamines and alkoxylated quaternary polyaniines which are disclosed in greater detail in the copending patent application of Patrick Delplancke et al., entitled "Aqueous, Gel, Laundry Detergent Composition", having P&G Case No. 6775, filed under the Patent Cooperation Treaty, Application No. PCTIUS98/15281 and intemational priority date July 23, 1998, hereby incorporated by reference.

The levels of these polyethoxyated-polyamine polymeTs used can r4nge from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight. 'Mese polyetboxyatedpolyamine polymers can be synthesized following the methodsoutline in U.S. Patent No. 4,664,848, or other ways known to those sl6lIed in the art.

Detersive Surfact2nts- Stnfictants are known to have potentially harsb effects on fabrics. Typically, the compositions herein will comprise from about 3 % to about 40 more Preferably frorn about 10 % to about 25 %, most preferably from about 15 % to about 20 by weight of detersive surEactants.

Nonlimiting examples of surfactants useful herein include tho unsaturated sulfates such as oleyl sulfate, the CIO-CjS alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), CIO-C18 aftl alkoxy carboxylates (especially the EO 1-5 ethoxymbor-Ylatcs), and Primary. branched-chain and random C10-C20 alkyl sulfates ("AS"), the CIO-C18 secondary (2,3) aftl sulfates of the formula CH3(CH2)x(CHOS03-M +) CH3 and CH3 (CH2)y(CHOS03-M +) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is 7695 a water-solubilizing cation, especially sodurn, the C10.1g glycerol ethers, the CIO-C18 alkyl polyglycosides and their corresponding sulfaied polyglycosides, and C1 2-C 18 alpha-sulforiated fatty acid esters.

If desired, the conventional nonionic and amphoteric surfactants such as the C12-Cl 8 alkyl ethoxylates CAR') including the so-called -narrow peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially etboxylates and mixed ethoxy/propoxy), C I 2-C 18 betaines and sulfobetaines ("sultaines"), CIO-C18 arnine oxides, and the like, can also be included in the overall compositions. The CIO-ClB N- alkylpolyhydroxy fatty acid amides can also be used. Typical examples includc thCCU-CMN-methylglucamides. SeeW09,206,154. Othersugarderived surfactants include the N-alkoxy polyhydroxy fatty acid arnides, such as C I O-C 1 g N-(3methoxypropyl) glucamide. The N-propyl through N-bexyl C12-C, g glucamides can be used for low sudsing. CIO-C2() conventional soaps may also be used. If high sudsing is desired, the branched-chain C I O-C 16 soaps may be used. Mixturcs of =ionic and nonionic surf4rtants are especially useful. Other conventional useful surfactants are listed in standard texts.

Folyh _ctant y4rox Fatty Acid Arnidc-LSAda - '11c detergent compositions hereof may a] so contain polyhydroxy fatty acid arnide surfactant. The polyhydroxy fatty acid amide surfactanx component comprises compounds of the structural formula:

0 R 11 1 R-C-N-Z Wherein: RI is H, C I -C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C 1 -C4 alkyl, rnore preferably C I or C2 alkyl, most preferably C 1 akl (i.e., methyl); and R2 is a C5- C31 hydrocarbyl, preferably straight chain C7-C 19 alkyl or alkenyl, more preferably straight chain C9-C 17 alkyl or alkeny], most preferably straight chain C I I -C 15 alkyl or a6lkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably etboxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z will be a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, marmose, and Xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These com syrups may yield a mix of sugar components for Z, It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH2- 16 7695 (CHOR)n-CH20H, -CH(CH20H)-(CHOMn,l-CH20H, -CH2-(CHOH)2(CHOR)(CHOMCH20H, and alkoxylated derivatives thereof, where n is an integer fTom 3 to 5, inclusive, and R! is H or a cyclic or alipbatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.

R'can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy cthyl, or N-2-hydroxy propyl.

R2-CO-N< can be, fbr example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitarnide, tallowarfde, etc.

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

Methods for making polyhydroxy fatty acid amides arc Imown in the art. In general, they can be made by reacting an alkyl arnine 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 t6glyceride in a condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amide6 are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by lbomas Hedley & Co., Ltd., U.S. Patent 2,965,576, issued December 20,1960 to E. R- Wilson, and U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of wbich is incorporated herein by reference.

Engymes - Suitable enzymes include prowases, amylases, lipases, cellulases, peroxidases, and mixtures tbereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active bleach, detergents, builders and the like. in this respect bacterial or fungal enzymes are preferred. such as bacterial arnylases and proteases, and fungal cellulases.

Enzymes can be included in the present detergent compositions for a variety of Purposes, including removal of protein-based, cubohydratebased, or tiiglyceride-based stains from surfaces such as textiles or dishcs, for the prevention of refugee dye transfor, for example in laundering, and for fabric restoration. EnZYmes are normaMy incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The terin "cleaning effcctive amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect an substrates such 17 7695 as dishware and the like. In practical terms for current cormncreial preparations, the compositions herein may comprise from 0.00 1 % to 5%, preferably 0.0 1 %-l% by weight of a commercial enzyme preparation. Protease enzyiiies arc 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 detersive enzyme and enzyme stabilizers are further disclosed in greater detail in the copending patent application of Eugene S. Sadlows1d, entitled "Aqueous, Gel, Laundry Detcrgent Composition!', having P&G Case No. 6955P, incorporated above.

EaMne Stabilizing System - Detergent compositions, particularly liquid detergent compositions, that include enzymes should also enzyme stabilizers and cblorine scavengers. The present invention may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weigbt of an enzyme stabilizing system. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition. See Severson, U.S. 4,537,706 for a review of Borate stabilizers.

Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide etc. Antioxidants such as carbarnate, ascorbate, etc., organic arnines such as ethylenediaminctetracetic acid (EDTA) or alkali metal salt thereof, monoethartolarnine (MEA), and mixtures thereof can likewise be used. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium Perborate tetrahydrate, sodium perborate monohydrate and sodium pcrcarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.

Polymeric DisRersing Agents - Polymeric dispersing agents can advantageously be utilized at levels frorn about 0. 1% to about 7%, by weight, in the compositions herein, especially in the presence of zcolite and/or layered silicate builders, Suitable Polymeric dispersing agents include Polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that Polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptizatim and anti-redeposition.

18 7695 Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates includc acrylic acid, maloic acid (or maltic anhydride), furnaric acid, itaconic acid, aconitic acid, mesaconic, acid, citraconic acid and methylenemalonic acid. Ile presence in the polymeric polyearboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the wa%T-solublc: salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges ftom about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most prefmbly from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, animonium and substituted ammonium salts. Soluble polymers of this type are known materials- Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in DieK U.S. Patent 3,309,067, issuea march 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-rcdeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The averagc molecular weight of swh copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably frorn about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally rangc from about 30:1 to about 1: 1, more PreferablY from about 10- 1 to 2:1. Watersoluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, antmonium and substituted ammonium salts. Soluble acrylatelmaleate copolymers of this type are known materials which are described in European Patent Application No- 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropYlacrylate. Still other useful dispersing agents include the maleic/acrylie/vinyl alcohol terpolYmers. Such materials are also disclosed in EP 193,360, including, for example, the 45145110 terpolyrner of acrylic/maleic/vinYl alcohol.

Other polymeric materials which can be included are polypropylene glycol (PPG), propylenc slycol (PG), and Polyethylene glycol (PEG), PEG can exIdbit dispersing agent perflormance as well as act as a clay soil removal-antiredeposition agent Typical molccular 19 7695 weight ranges for these purposes range from about 5 00 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1, 500 to about 10,000.

Polyaspartate and polyglutarnate dispersing agents may also be used, especially in conjunction with zeolitc builders. Dispersing agents such as polyaspartate preferably have a molccular weight (avg.) of about 10, 000.

Alkoxylated polycarboxylates such as those prepared Erom polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91108281 and PCT 90/01915 at p- 4 et seq. Chemically, these materials comprise polyacrylates having one ethoxy sidechain per every 7-8 acrylate units, The side-chains am of the formula (CH2CI420)rn(CH2)nCH3 wberein in is 2.3 and n is 6-12. The side-chains arc ester-linkcd to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions hcrein.

The levels of these dispersants used can range from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight. These dispersants can be synthesizcd following the methods outline in US - Patent No. 4,664, 84.8, or other ways known to those skilled in the art.

DyS Fixative Materials - optionally but preferred for use herein arc selected dye fixative materials which do not form precipitates with anionic surfactant.

The selected dye fixatives useful herein may be in the form of unpolymerized materials, oligomers or polymers. Moreover, the preferred dye fixatives useful herein arc cationic. The dye fixative component of the compositions herein will generally comprise from about 0.1% to 5% by the weight of the composition. More preferably, such dye fixative materials will compise from about 0.5% to 41/6 by weight of the compositions, most preferably from about I% to 3%. Such concentrations should be sufficient to provide from about 10 to 100 ppm of the dye fixative in the aqueous washing solutions formed from the laimdry detergent compositions hereiri. More preferably from about 20 to 60 ppm of the dye fixative will be delivered to the aqueous washing solution, most prefembly about 5 0 ppin.

The non-precipitating dye fixatives useful berein include a number that are commercially marketed by CLARIANT Corporation under the Sandofix(ID, SandolecO and Polymer VRN'0 trade names. These include, for example, Sandofix SWEO, Sandofix WAO, Sandolec CTO, Sandolec CSO, Sandolec CIO, Sandolec CFO, Sandoler. WAe and Polymer VRNO. Other 7695 suitable dye fixatives are marketed by Ciba-Geigy Corporation under the trade name Cassofix FRN-3008 and by Hoechst Celanesc Corporation under the U-ade name Tinofix EVIO, Polymeric Soil Release Agent- Soil release agents may be used in the present invention, If so they will generally comprise from about 0.01 % to about 10.0%, by weight, of the dctergent compositions herein, typically from about 0. 1% to about 5%, preferably from about 0.2% to about 3.0%.

Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and -processes of this invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and its blends, and bydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thcreto through completion of washing and rinsing cycles and thus, serve as an anchor for the hydropbilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

The polymeric soil release agents useful herein especially include those soil release agents having-, (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylenc or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylenc units comprising oxyethylene and from I to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophilo component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylenc units, at least about 50% oxyethylene units; or (b) one or more hydrophobe componcrits comprising (i) C3 oxyalkylene terephthalate segrnents, wherein, if said hydrophobe components also comprise oxyethylene tercphthalate, the ratio of OxYethYlenc terephthalate-.C3 oxyalkylene tereplithalate units is about 2.1 or lower, 00 C4-C6 alkylene or oxy C4- C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, Or Ov) C I -C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C I -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and sucb cellulose derivatives arc amphiphilic, whereby they have a sufficient level of C I -C4 21 7695 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of bydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Other suitable polymeric soil release agents arc disclosed in U.S. Patent No. 5,415,807, issued May 16, 1995 to Gosselink, which is hereby incorporated by reference.

Dyp Transfer Inhibiting A -,ents-The compositions of the present invention rnay also include one or more materials effective for inhibiting the transfer of dyes ftom one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyarnine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixt=s thereof. If used, these agcnts typically comprise from about 0.0 1% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2% More specifically, the polyarnine N-oxide polymers pref=ed for use herein contain units having the following structural formula: R-Ax-P; wherein F is a polymerizable unit to which an N-0 group can be attached or the N-0 group can form part of the polymcrizable unit or the N-0 group can be attached to both units; A is one of the following structures: -NC(O)-, - C(0)0-, -S.' 0-, -N=- x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combinati(m thereof to which the nitrogen of the N-0 group can be attached or the N-0 group is part of these groups. Preferred polyarnine N- oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazolc, pyrrolidine, piperidine and derivatives thereof, The N-0 group can be represented by the following general sbructures., 0 ? I (Rj)X-N-(R2)y; ==N-(RI)x I (R3)Z wherein RI, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof-, x, y and z are 0 or 1; and the nitrogen of the N-0 group ran be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa --,7, more preferred pKa <6.

Any polymer backbone can be used as I ong as the amine oxide polymer formed is watersoluble and has dye transfer inhibiting propcrties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylatcs and 22 7695 mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an Noxide, The arnine N-oxide polymers typically have a ratio of aminc to the aniine N-oxide of 10, 1 to 1: 1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymcaization or by an appropriate degree of N-oxidation. Ile polyamine oxides can be obtainod in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. Preferred polyamine N-oxide are discussed in greater detail in U.S- Patent No. 5,466,802, issued Nov. 14, 1995 to Pariandiker, which is bercby incorporated by reference Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI bas an average molecular weight range from 5,000 to 1,000,000, more preferably froin 5,000 to 200,000, and most prefcrably from 10,000 to 20,000, Preferred copolymers of N-vinylpyrrohdone and Nvinylin:iidazole polymers are discussed in greater detail in U.S. Patent No. 5,466,802, incorporated above.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-7.62,897 and EP-A- 256,696, incorporated herein by reference- Compositions containing PVP can alsocontain polyethylene glycol ("PEG") having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2-1 to about 50:1, and more preferably from about 3:1 to about 10.1.

Bri - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.01% to about 1.20%, by weight into the detergent compositions herein. Conunercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5 -dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. 'Examples of such brighteners are disclosed in "The Producon and Application of Fluorescent Brightening Agents", M. Zahradnik Published by John Wilcy & Sons, New York (1982).

23 7695 Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,956, issued to Wixon on December 13, 1988. These brigbteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal LTNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic Wliite CWD, the 2-(4-styrylphenyl)-2H-napthofl,2d]biazoles; 4,4!-bis-(1,2,3-tiazol-2-yl)-stilbenes; 4,W-bis(styryl)bisphenyls; and the aminocoumarins. See also U.S. Patent No. 3,646,015, issued February 29,1972 to Hamilton and U.SPatent No. 5, 466,802, incorporated above.

Suds Supmessors - Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4, 489,455 and 4,489,574 and in frontloading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encornpasscs monocarboxylic. fatty aLcid and soluble salts therein. Sce U-S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atorm, preferably 12 to 18 carbon atoms- Suitable salts include the alkali metal salts such as sodiunni, potassium, and lithium salts, and arnrnonium and alkanolanunoniurri salts.

The detergent compositions herein may also contain rion-surfactant suds suppressors. These include, for example; high molecular weight hydrocarbons, N-alkylated amino triazines, monostcaTyl phosphates, silicone suds suppressors, secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. Silicone suds suppressors are well Imown in the art and are, for example, disclosed in U.S- Patcrit 4265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307951.9, published February 7, 1990, by Starch, M. S. Mixtures of alcohols and silicone oils are described in U.S. 4,798,679, 4,075,118 and EP 150,872 Additional examples of all of the aforementioned suds suppressors rnay be found in fl= provisional patent application of Pramod K. Reddy, entitled "Hydrophilic Index for Aqueous, Liquid Laundry Detergent Compositions containing LAS", filed under the Patent Cooperation 24 7695 having P&G Case No. 7332P, filed on November 6, 1998 and having Serial No 60/107,477, which is hereby incorporated by reference.

Alkoxylated Po1yca.Tbg2MIAWg - Alkoxylated polycarboxylates such as those preparcd from polyacrylates are useful herein to provide additional grease removal performance. Such materials arc described in WO 91/08281 and PCT 901018 15 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side- chain pcr every 7-8 acrylate units. The side-chains are of the formula (CH2CH20)m(CH2)nCH3 wherein rn is 2-3 and n is 6-12. 'Me side-chains are estcr-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the Tange of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.

QAonal Campo Lents-The compositions herein may further contain one or more additional detersive additives selected from the group consisting of polymeric dispersing agents, dycs, colorants, filler salts, through-thewash fabric softeners, antiredeposition agents, antifading agent, dye fixative agents, prill/Aizzing reducing agents, and mixtures thereof.

Method Asplet Tle compositions of this invention can be used to form aqueous washing solutions for use in the laundering of fabrics. Generally, an effective amount of such compositions is added to water, pi-cferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith.

An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 3,000 pprn of the detergent compositions herein will be provided in aqueous washing solution.

The following examples are illustrative of the present invention, but are not meant to lint or otherwise define its scope. All parks, percentages and ratior. used herein are expressed as percent weight unless otherwise specified.

7695 FMAWLES Table I

Liquid laundry detergent compositions of the present invention are as follows:

Example A B C D E F AE2.5S' 21 21 20.2 22-7 22,7 13.6 C12LAS - - - - 9.1 C12-14 glucosamide 4 4 2.5 - AE072 4.5 4.5 - - AE093 - - 0.6 0.6 0.6 0.6 Cs-,,) ainidopropylamine 1.3 1.3 - - - - C I D amidopropylarnine - - 1.3 1.3 1.3 1.3 citric acid 1 3 5 1 25 1 C12-14 fatty acid - - 10 10 8 10 palm kernal fatty acid 8 5.4 - - - - rapeseed fatty acid 8 5.4 - - - protease 0.6 0.6 0.9 0.9 0.9 0.9 lipasc 0.07 0-07 0.08 0.08 0.08 0.08 amylase 0.19 0.18 0.15 0.15 0,15 0.15 cellulase 0.03 0.03 0.05 0.05 0.05 0.05 endolase 0.2 0.2 - - - brightener 0.15 0.15 0.15 0.15 0.15 0.15 polymer A' 0.66 0.66 0.6 0.6 0-6 0.6 polymer B 5 - 1.2 1.2 1.2 1.2 Polyamine-polyarnide 2 1 1 - Polyethoxylated-Polyamincs - 1 2 - - soil release agent - 0.1 0.1 0.1 0.1 ethariol 0,7 0.7 0.54 0.54 0.54 0.54 1,2-propanediol 4 4 4 4 4 4 Monoethanolarnine -0.7 o.7 0.5 0.5 0.5 0.5 NaOH 2.8 2.8 7 7 7 7 boric acid 2 2 26 7695 borax 2.5 2.5 2.5 2.5 suds supressor 0.1 0.1 0.1 0.1 PDMS 0.2 0.2 - - perfurne composition 7 0.5 0.5 0.75 0.75 0.75 0.75 dye - - 0.04 0.04 0.04 0.04 0, 0,04 water balance balance balance balance balance balance 1: C12-15 alkyl ethoxysulfonate containing an average of 2.5 ethoxy groups 2- C,2.,. Alkyl ethoxylated surfactant containing seven etboxy groups. 3-C,2,1.sAlkylethoxylated surfactant containing nine ethoxy groups, 4.- Modified polyarnines of PEI (MW = 182) with average degree of ethoxylation 15 5-, Modified polyarnines of PEI (MW = 600) with avenge degree of ethoxylation 20 6: The polyarnine-polyarnides selected from those compounds marketed under the following tradc names: KyrneneqD, Kyrnene 5 5 7HO, Kyrnenc 5 5 7LXS, Reten@, and CartaretinQD 7: The perfurne Composition is selected from the perfume compositions A - I described in table IV (below).

27 ?695 Table U Liquid laundry detergent compositions of the present invention are as follows:

Example Number G H I i AE2.5S' 19.12 18.25 22.65 22.65 C12 LAS 4.5 AF-092 o.6 5 0.6 0.6 Clo amidopropylanne 1.3 1.3 1.3 1 1.3 citric acid 1 1 1 1 C,2.,, fatty acid 10 10 10 10 Quaternary Surfactad 0.5 1 5 - oleic acid - - 2.5 protease 0.9 019 0.9 0.9 lipase 0.08 0.09 0.08 0.08 amylase 0.15 0.15 0-15 0.15 cellulase 0.05 0.05 0.05 0.05 brightener 0.15 0.15 0.15 0.15 polymer A 0.6 0.6 0.3 0.6 polymer 1.2 1.2 0-6 1.2 soil release agent 0.1 0.1 0.1 0.1 ethanol 0.54 0.54 0.54 0.54 1,2-propanediol 4 4 4 4 Monoethanolarnine 0.48 0.48 0.48 0.48 NaOH 7 7 7 7 borax 2.5 2.5 2.5 2.5 suds supressor 0.1 0.1 0.1 0.1 perfume composition 6 0.75 0.75 0.75 0.75 dye 0.04 0.04 0.04 0.04 water ta-l ance hAlance balance balance 1: C12.15 alkyj ethoxy sulfonate containing an avcrage of 2.5 ethoxy groups 2,: C12.15 Alkyl ethoxylated surfactant containing nine ethoxy groups.

28 7695 3 - Quaternary Surfactant is selected from one or more of the following: lauryl trirnethyl ammonium chloricic, myristyl trimethyl arrurioniurn chloride, palmityl trimethyl an=om'um chloride, coconut trimethylammonium chloride, coconut trimethylanvnonium rnethylsulfate, coconut dirnethyl- monchydroxyethyl-ammonimn chloride, coconut dimethylmonohydroxyethylarrimoniurn methylsulfate, steryl dimethylmonobydroxy-ethylammonium chloride, steryl dimethylmonohydroxyethylammoniuTn methylsulfate, di- C I 2-C 14 alkyl dimethyl amznonium chloride.

4: Modified polyamines of PEI (MW 182) with average degree of cthoxylation = 15 5: Modified polyamincs of PEI (MW 600) with average degree of ethoxylation = 20 6: The perfume Composition is selected from the perfume compositions A - I described in table IV (below).

Table M

Liquid laundry detergent co ositions the present invention an as follows:

ExWRle Number K L M AE2.5S' 27.65 22.65 22,65 citric acid I I I C12 4 4 fatty acid 7.5 5 10 protease 0.9 0.9 0.9 lipase 0.08 0.08 0.08 amylase 0.15 0.15 0.15 cellulase 0.05 0.05 0.05 brightener 0.15 0.15 0.15 polymer A 0.6 0.6 0.6 polymer B' 1.2 1.2 1.2 soil release agent 0.1 0.1 0.1 ethanol 0.54 0.54 0.54 1,2-propanediol 4 4 4 Monoethanolamine "4 OA8 0.48 NaOH 7 7 7 borax 2.5 - 2.5 suds supressor 0.1 F 1.1 0.1 29 7695 perfume composition' 0.75 0.75 0.75 dye 0.04 0.04 0.04 water balance balance balance 1: C12.13 alkyl ethoxy suffonate containing an average of 2.5 ethoxy groUps 2, C12_15 Alkyl, ethoiylated surfactant containing nine ethoxy groups.

3: Modified polyamines of PEI (MW = 182) with average degree of ethoxylation = Is 4: Modified polyannes of PEI (MW = 600) with average degree of ethoxylation = 20 5: The perfume Composition is selected from the perfume compositions A - I described in table IV (below).

Fragrance Material -Weight Table IV

Perfume compositions of the present invention are as follows:

Eragrance Material A B C D E F G H I dihydromyreenot 20 0 10 0 10 10 10 18 18 lilial 20 10 10 20 5 10 10 18 18 iso E super 10 10 0 0 0 5 5 9 9 vertenex 10 10 3 0 0 5 5 9 9 ionone Garnma methyl 10 10 10 10 0 5 5 9 9 bexyl cinnamic aldehyde 10 20 10 20 20 5 5 9 9 ionone, beta 5 4 0 0 0 2.5 2.5 4.5 4.5 baba-nolide 5 5 40 10 0 2.5 2.5 4.5 4.5 flor acetate 3 3 3 3 0 1.5 1.5 2.7 2.7 polysantol 3 2 2 3 0 1.5 1.5 2.7 2.7 fiutene 2 2 2 0 0 1 1 1.8 1.8 alpha pinene 1 2 0 2 3 0.5 0.5 0.9 0.9 camphene 1 2 0 2 2 0.5 0.5 0.9 0.9 d4imonen 0 20 0 0 40 0 0 0 0 tetrahydro linalool 0 0 10 30 20 0 0 0 0 geranjol 0 0 0 0 0 20 5 0 linalool 0 0 0 0 0 10 10 0 0 phenyl ethyl alcohol 0 0 0 0 0 20 15 5 10 cetate 0 0 0 0 0 0 5 0 0 7695 1 Eucalyptol 0 0 0 0 0 0 5 0 0 Total 100 1 tLI 100 100 100 105 100 100 1 31 7695/VB

Claims (11)

What is claimed is:

1. A heavy duty gel or liquid laundry detergent composition characterized by, by weight of the composition; a) from 10% to 40% of an anionic surfactant; b) a perfume composition, wherein at least I % of the perfume composition is characterized by fragrance materials selected from the group consisting of fragrance materials having a logP of at least 3; and c) a structurant.

2. The detergent composition of Claim I whercin the detergent composition is transparent.

3. The detergent composition of any of Claims 1-2 wherein the viscosity of the detergent composition is from 100 cps to 4,000 cps when measured at a temperature of 25C and at a shear rate of 20 s " -

4. The detergent composition of any of Claims 1-3 wherein the composition is wholly or partly in larnellar form.

5. The detergent composition of any of Claims 1-4 wherein the structurant is characterized by an electrolyte and a detergent builder, and the ratio of electrolyte to detergent builder is from 10:1 to 1:10.

6. The detergent composition of any of Claims 1-5 wherein the perfume composition further is characterized by from I % to 90% of a fragrance matcrial having a boiling point of at least 250' C.

7. A heavy duty liquid or gel laundry detergent composition which is either wholly or partly in lamcllar form and is characterized by, by weight of the composition:

a) from 10% to 40% of an anionic surfactant; b) from 0. 1 % to 3.0% of a perfume composition, wherein at least 1.0% of the perfume composition is characterized by fragrance materials selected from the group consisting of fragrance materials having a logP of at least 3; C) at least 0.5% of a structurant; and 32 J UL---) I -,::ULIJVJ 10 - r OxLa r rIt 1 r.1 I I I I 111 Lir- I U-j I 7695ArB d) an amine selected from the group consisting of detersive arnines, modified polyamines, polyarnide-polyarnines, polyetboxylated-polyaTnine polymers, quaternary ammonium surfactants, and mixtures thereof; wherein the viscosity of the detergent composition is from 100 cps to 4,000 cps when measured at a temperature of 2SC and at a shear rate of 20 s

8. The detergent composition of any of Claims 1-7 whcrcin the perfume composition further comprises from 1% to 90% of a fragrance material having a boiling point of at least 250 C.

9. The detergent composition of any of Claims 1-8 wherein the structurant comprises an electrolyte and a detergent '-uilder, and the ratio of electrolyte to detergent builder is from 10: 1 to

10. A detergent composition substantially as described herein with reference to the examples.

11. A method of cleaning a textile fabric characterised by the steps of (i) preparing a liquid or gel laundry detergent composition according to any of claims I to 10 (ii) dissolving an effective amount of the detergent composition in water to form an aqueous solution; and (iii) contacting the textile fabric with the aqueous solution.

33 TnTOI P VA7