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Title:
POLYHYDROXY AMIDES TO PROVIDE DYE TRANSFER INHIBITION BENEFITS DURING FABRIC LAUNDERING
Document Type and Number:
WIPO Patent Application WO/1995/023840
Kind Code:
A1
Abstract:
Dyed fabrics are laundered with N-alkyl or N-alkoxy polyhydroxy fatty acid amide surfactants with minimal dye transfer between fabrics. Thus, a laundry bath comprising C12-C14 N-methyl glucamide provides dye transfer inhibition on laundered fabrics. Additional dye transfer inhibiting agents such as poly(4-vinylpyridine-N-oxide) may be used in the compositions for improved results.

Inventors:
BROWN DONALD RAY
MANOHAR SANJEEV KRISHNADAS
Application Number:
PCT/US1995/002218
Publication Date:
September 08, 1995
Filing Date:
February 23, 1995
Export Citation:
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Assignee:
PROCTER & GAMBLE (US)
International Classes:
D06L1/12; C11D1/52; C11D3/00; C11D3/37; C11D17/08; D06M13/02; D06M13/322; D06M13/419; D06M15/59; (IPC1-7): C11D1/52; C11D3/37
Domestic Patent References:
WO1994002580A11994-02-03
WO1995007332A11995-03-16
WO1992006172A11992-04-16
Foreign References:
GB1348212A1974-03-13
Other References:
DATABASE WPI Section Ch Week 9150, Derwent World Patents Index; Class A96, AN 91-365819
Download PDF:
Claims:
WHAT IS CLAIMED IS:
1. A method for laundering dyed fabrics with minimal dye transfer, characterized in that it comprises contacting said fabrics with an aqueous medium which contains at least 100 ppm of a polyhydroxy amide surfactant which is a member selected from the group consisting of compounds of the formula: (I) and (II) O R4 r,, 'I I R3CN— Z wherein in formulas (I) and (II): R3is C7Q21 hydrocarbyl, R1 is C2Cs hydrocarbyl; R2 is CjCg hydrocarbyl; R4 is CiCβ alkyl or hydroxyalkyl; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
2. A method according to Claim 1 wherein the polyhydroxy amide surfactant has substituent Z derived from glucose.
3. A method according to Claim 2 wherein substituent R!"OR on said surfactant (I) is 3methoxypropyl.
4. A method according to Claim 2 wherein substituent R4 on said surfactant (II) is methyl.
5. A method according to Claim 1 wherein said aqueous medium additionally contains at least 1 ppm of a dye transfer inhibiting agent which is a member selected from the group comprising of polyamine Noxides, copolymers of Nvinylpyrrolidone with Nvinylimidazole, polyvinylpyrrolidone, hydrophilic optical brighteners, and mixtures thereof.
6. A method according to Claim 5 wherein said dye transfer inhibiting agent is a mixture of a polyamine Noxide and a copolymer of Nvinylpyrrolidone and Nvinylimidazole.
7. A laundering composition especially adapted for laundering dyed fabrics with minimal dye transfer, characterized in that it comprises: (a) at least 2% by weight of a polyhydroxy amide surfactant which is a member selected from the group consisting of compounds of the formula: (I) and (II) O R4 m II I R3CNZ wherein in formulas (I) and (II): R3 is C7C21 hydrocarbyl; R is C2C.
8. hydrocarbyl; R2 is CjCg hydrocarbyl; R4 is CjCg alkyl or hydroxyalkyl; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. (b) at least 0.01% by weight of a dye transfer inhibiting agent which is a member selected from the group consisting of polyamineNoxides, copolymers of Nvinylpyrrolidone with Nvinylimidazole, polyvinyl pyrrolidone, hydrophilic optical brighteners, and mixtures thereof; (c) optionally, an anionic surfactant; (d) optionally, a detergency builder; (e) optionally, an enzyme selected from proteases, cellulases, Upases, amylases, peroxidases and mixtures thereof; and (f) optionally, a bleach.
9. 8 A composition according to Claim 7 wherein the polyhydroxy amide surfactant is of formula (I), wherein Rl"OR2 is 3methoxypropyl and Z is derived from glucose.
10. A composition according to Claim 7 wherein the polyhydroxy amide surfactant is of formula (II) wherein R4 is methyl or hexyl and Z is derived from glucose.
11. A composition according to Claim 7 wherein said dye transfer inhibiting agent is a mixture of a polyamine Noxide and a copolymer of N vinylpyrrolidone and Nvinylimidazole. dr.
Description:
POLYHYDROXY AMIDES TO PROVIDE

DYE TRANSFER INHIBITION BENEFITS

DURING FABRIC LAUNDERING

FIELD OF THE INVENTION The present invention relates to the use of polyhydroxy amide surfactants, optionally in combination with various additional agents, to inhibit dye transfer from and between fabrics during laundering.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of co-pending application serial number 08/206,557, filed March 4, 1994.

BACKGROUND OF THE INVENTION The formulation of effective laundry detergent compositions which are sufficiently robust to remove a wide variety of soils and stains from fabrics under a variety of usage conditions is a major objective of the industry. Conversely, optimal laundry detergents should be formulated with ingredients which do not detract from the overall appearance of the fabrics being laundered. In regard to this latter point, the undesirable removal of dyes from fabrics is of special concern to the detergent formulator. Dye removal diminishes the appearance of the fabrics. Moreover, vagrant dye molecules present in the wash liquor can undesirably deposit onto other fabrics, a phenomenon which is commonly referred to as "dye transfer". Thus, the formulator is faced with the considerable challenge of providing high performance compositions which clean well, but with minimal dye transfer.

Most conventional detergent compositions contain mixtures of various detersive surfactants in order to remove a wide variety of soils and stains. For example, various anionic surfactants, especially the alkyl benzene sulfonates, are useful for removing paniculate soils, and various nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates are useful for removing greasy soils. Accordingly, mixtures of anionic and nonionic surfactants are used in many modern detergent compositions. While a review of the literature would seem to suggest that a wide selection of surfactants is available to the detergent manufacturer, the reality is that many such materials are specialty chemicals which are not suitable for routine use in low unit cost items such as home laundering compositions. The fact remains that most home-use detergents still comprise one or more of the conventional ethoxylated

nonionic and sulfated or sulfonated anionic surfactants. Accordingly, dye transfer remains problematic in many such products.

One approach in attacking the dye transfer problem in laundering operations has been to complex or adsorb the fugitive dyes washed out of dyed fabrics before such dyes have the opportunity to become attached to other articles in the wash solution. Certain polymeric materials, for instance, have been suggested as being useful laundry detergent additives which can complex or adsorb fugitive dyes in aqueous washing solutions. For example, Abel, U.S. Patent 4,545,919, issued October 8, 1985, describes the use of carboxyl-containing polymers in fabric laundering operations. Waldhoff et al., DE-A-2 814 329, published October 11, 1979, discloses the use of N-vinyl-oxazolidone polymers and Cracco et al., GB 1,348,212, published March 13, 1974, discloses the use of 15-35% of a copolymer of polyvinylpyrrolidone and acrylic acid nitrile or maleic anhydride within a washing powder. Clements et al., EP-A-265 257, published April 27, 1988, describes detergent compositions comprising an alkali-metal carboxy-metal carboxymethylcellulose, a vinylpyrrolidone polymer and a polycarboxylate polymer.

Notwithstanding prior art attempts to solve the dye transfer problem during fabric laundering, there is a continuing need to identify detergent compositions, detergent composition additives and fabric laundering methods which are especially effective against dye transfer. Accordingly, it is an object of the present invention to provide detergent compositions which contain ingredients that eliminate or at least minimize dye transfer between fabrics when such compositions are used in fabric laundering operations.

It is a further object of the present invention to provide such especially effective dye transfer-inhibiting detergent compositions in either granular or liquid form.

It is a further object of the present invention to provide a method for laundering colored fabrics in aqueous washing solutions which are formed from the detergent compositions herein and which thereby contain materials that eliminate or at least minimize dye transfer between fabrics being washed therein.

By the present invention, it has been discovered that certain polyhydroxy amide surfactants can be used to minimize dye transfer during a laundering operation. This discovery is particularly advantageous, inasmuch as the polyhydroxy amide surfactants herein also have additional properties which are advantageous to the detergent formulator. For example, these surfactants are biodegradable, mild to skin and fabrics, exhibit low interfacial tensions, provide excellent oily soil removal

properties, and can be manufactured mainly from renewable, non-petrochemical resources such as sugars, and animal or vegetable fats and oils.

BACKGROUND ART U.S. 5,194,639 and Japanese Kokai HEI 3[1991]-246265 Osamu Tachizawa, U.S. Patents 5,174,927 and 5,188,769 and WO 9,206,171, 9,206,151, 9,206,150 and 9,205,764 relate to various polyhydroxy fatty acid amide surfactants and uses thereof.

SUMMARY OF THE INVENTION

The present invention encompasses a method for laundering dyed fabrics with minimal dye transfer comprising contacting said fabrics with an aqueous medium which contains at least about 100 ppm, preferably from about 160 to about 2000 ppm, of a polyhydroxy amide surfactant which is a member selected from the group consisting of surfactant compounds of the formula (I) or (II), as described hereinafter, or mixtures thereof. The preferred method is wherein said aqueous medium additionally contains at least about 1 ppm, preferably from about 3 to about 20 ppm, of a dye transfer inhibiting agent which is a member selected from the group consisting of "PVNO", "PVPVI", "PVP" and brightener type agents and mixtures thereof, all as described more fully hereinafter.

The invention also encompasses laundering compositions especially adapted for laundering dyed fabrics with minimal dye transfer, comprising: (a) at least about 2%, preferably from about 2% to about 50%, by weight of a polyhydroxy amide surfactant which is a member selected from the group consisting of compounds of the formula (I) or (II), or mixtures thereof;

(b) at least about 0.01% by weight of a dye transfer inhibiting agent which is a member selected from the group consisting of PVNO, PVPVI,

PVP and brightener-type agents, and mixtures thereof;

(c) optionally, an anionic surfactant;

(d) optionally, a detergency builder;

(e) optionally, an enzyme selected from proteases, cellulases, lipases, amylases, peroxidases and mixtures thereof; and

(f) optionally, a bleach.

One type of preferred composition and method herein is where the polyhydroxy amide surfactant is of the formula (I), wherein R is -CH2-CH2-CH2, R 2 is -CH3, R 3 is C\ 1-C17 alkyl or alkenyl and Z is derived from glucose. Another preferred composition and method herein is where the polyhydroxy amide surfactant is of formula (II), wherein R 3 is Cn-Cj alkyl or alkenyl and wherein R^ is methyl or (for low sudsing) hexyl.

Highly preferred compositions of the foregoing type are those wherein the dye transfer inhibiting agent is PVPVI, PVNO or brighteners, all as described more fully hereinafter.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are, in relevant part, incorporated herein by reference.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a series of graphs which illustrate dye transfer results on cotton fabric as a function of surfactant type and concentration. The data are reported as delta E values. The smaller the delta E value, the less dye transfer has occurred. The graphs are clustered in groups of three and illustrate the use of the test surfactants at concentrations of 160 ppm (cross-hatched), 800 ppm (white) and 1600 ppm (cross- hatched), as shown in the Key, respectively. The following surfactant types are shown in the graphs: LAS (alkyl benzene sulfonate, control); AS (C14-.15 alkyl sulfate); AE (coconut-alkyl ethoxylate with an average 3 ethoxy units); PFAA (Cj2- 14 N-methyl glucamide of this invention); LAS (repeat of alkyl benzene sulfonate, control); SAS (Cj6 secondary alkyl sulfate); AES (Ci2-13 alkyl ethoxy [3] sulfate); alkoxy PFAA (mixed palm fatty acids N-(3-methoxy propyl) glucamide of this invention). Details of the tests relating to Figure 1 are described in the Experimental section, hereinafter. DETAILED DESCRIPTION OF THE INVENTION

Fattv Acid Amide Surfactants The N-alkoxy, N-aryloxy polyhydroxy fatty acid amide surfactants used herein comprise materials of the formula (I):

O R — O— R2

R3— C-N— Z (I) The N-alkyl polyhydroxy fatty acid amide surfactants used herein comprise materials of the formula (II):

O R4 II I R3— C-N-Z (||) wherein in formulas (I) and (II): R 3 is C7-C21 hydrocarbyl, preferably C9-C17 hydrocarbyl, including straight-chain and branched-chain alkyl and alkenyl, or mixtures thereof; R is C2-Cg hydrocarbyl including straight-chain, branched-chain and cyclic (including aryl), and is preferably C2-C4 alkylene, i.e., -CH2CH2-, - CH2CH2CH2- and -CH2(CH2)2CH2-; R 2 is selected from Ci-Cg straight-chain, branched-chain and cyclic hydrocarbyl including aryl and oxy-hydrocarbyl, and is preferably C1-C4 alkyl or phenyl; R 4 is Cj-C6 alkyl or hydroxyalkyl, including

methyl (preferred), ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-hydroxyethyl, 3- hydroxypropyl, and the like; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a 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 -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n . 1 - CH 2 OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 1 to 5, inclusive, and R 1 is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2- (CHOH) 4 -CH 2 OH.

In compounds of the above formula (I), nonlimiting examples of the amine substituent group -R1-0-R 2 can be, for example: 2-methoxyethyl-, 3- methoxypropyl- (preferred), 4-methoxybutyl-, 5-methoxypentyl-, 6-methoxyhexyl-, 2-ethoxyethyl-, 3-ethoxypropyl-, 2-methoxypropyl, methoxybenzyl-, 2- isopropoxyethyl-, 3-isopropoxypropyl-, 2-(t-butoxy)ethyl-, 3-(t-butoxy)propyl-, 2- (isobutoxy)ethyl-, 3-(isobutoxy)propyl-, 3-butoxypropyl, 2-butoxyethyl, 2- phenoxyethyl-, methoxycyclohexyl-, methoxycyclohexylmethyl-, tetrahydrofurfuryl-, tetrahydropyranoxyethyl-, 3-[2-methoxyethoxy]propyl-, 2-[2-methoxyethoxy] ethyl-,

3-[3-methoxypropoxy]propyl-, 2-[3-methoxypropoxy] ethyl-, 3-

[methoxypolyethyleneoxyjpropyl-, 3-[4-methoxybutoxy]propyl-, 3-[2-methoxy- isopropoxyjpropyl, CH 3 O-CH 2 CH(CH 3 )- and CH 3 OCH 2 CH(CH3)CH2-O-(CH2)3.

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

While the synthesis of N-alkoxy, N-aryloxy or N-alkyl, alkenyl and hydroxyalkyl polyhydroxy fatty acid amides can prospectively be conducted using various processes, contamination with cyclized by-products and other colored materials may be problematic. As an overall proposition, the synthesis method for these surfactants can comprise reacting the appropriate N-substituted aminopolyols with fatty acid methyl esters or fatty acid glycerides with or without a solvent, but preferably using methanol or an ethoxylated alcohol such as NEODOL as a solvent,

using an alkoxide catalyst at temperatures of about 85°C to provide high yields (90- 98%) of the products having desirable low levels (preferably, less than about 10%) of ester amide or cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2. See, for example, U.S. Patent 5,194,639 to Connor, Scheibel and Severson, issued March 16, 1993. If desired, any unreacted amino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, in water at 50°C-85°C to minimize the overall level of such residual amines in the product. Residual sources of straight-chain primary fatty acids, which can suppress suds, can be depleted by reaction with, for example, monoethanolamine at 50°C- 85°C.

If desired, the water solubility of the solid N-alkoxy polyhydroxy fatty acid amide surfactants herein can be enhanced by quick cooling from a melt. While not intending to be limited by theory, it appears that such quick cooling re-solidifies the melt into a metastable solid which is more soluble in water than the pure crystalline form of the N-alkoxy polyhydroxy fatty acid amide. Such quick cooling can be accomplished by any convenient means, such as by use of chilled (0°C-10°C) rollers, by casting the melt onto a chilled surface such as a chilled steel plate, by means of refrigerant coils immersed in the melt, or the like. By "cyclized by-products" herein is meant the undesirable reaction by¬ products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substituents) is naturally "capped" by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein. The following illustrates the syntheses in more detail. Preparation of Ci -N-O-MethoxypropyOglucamide - N-(3-methoxy- propyl)glucamine, 1265 g (5.0 mole) is melted at 140°C under nitrogen. A vacuum is pulled to 25 inches (635 mm) Hg for 10 minutes to remove gases and moisture. Propylene glycol, 109 g (1.43 mole) and CE 1295 methyl ester, 1097 (5.1 mole) are added to the preheated amine. Immediately following, 25% sodium methoxide, 54 g (0.25 mole) is added in halves. Reactants weight: 2525 g

Theoretical MeOH generated: (5.0 x 32) + (0.75 x 54) + (0.24 x 32) = 208.5 g

Theory product: FW 436 2180 g 5.0 mole

The reaction mixture is homogeneous within 1 minute of adding the catalyst. It is cooled with warm H2O to 85°C and allowed to reflux in a 5-liter, 4-neck round bottom flask equipped with a heating mantle, Trubore stirrer with Teflon paddle, gas inlet and outlet, Thermowatch, condenser, and air drive motor. When catalyst is added, time = 0. At 60 minutes, a GC sample is taken and a vacuum of 7 inches (178 mm) Hg is started to remove methanol. At 120 minutes, another GC sample is taken and the vacuum has been increased to 12 inches (305 mm) Hg. At 180 minutes, another GC sample is taken and the vacuum has been increased to 20 inches (508 mm) Hg. After 180 minutes at 85°C, the remaining weight of methanol in the reaction is 2.9% based on the following calculation: 2386 g current reaction wt. - (2525 g reactants wt..- 208.5 g theoretical MeOH)/2386 g = 2.9% MeOH remaining in the reaction. After 180 minutes, the reaction is bottled and allowed to solidify at least overnight to yield the desired product. Preparation of Fattv Acid N-alkyl glucamides - Following the procedures of

U.S. 5,194,639, coconut alkyl (C12- 14) or other fatty acid methyl esters are reacted with N-methyl glucamine using methanol solvent and sodium methoxide catalyst in a convenient synthesis of the fatty acid N-methylglucamide surfactant of the type used herein. Dve Transfer Inhibiting Agents

The compositions of the present invention optionally, but preferably, include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% 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 polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those

wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures:

O O

(R 1 )x-N-(R 2 ) y = N-(R 1 ) X

( 3 )z wherein K\, 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-O group can 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 long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and 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 N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine 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 copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained 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. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113. "Modem Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

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-262,897 and EP-A-256,696, incorporated herein by reference. Compositions containing PVP can also contain 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.

Mixtures of PVNO and PVPVI are especially useful herein, typically at a weight ratio in the range from about 3:1 to about 1:3, and are particularly useful at levels of from about 0.05% to about 0.15%, by weight, of the compositions.

The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

wherein Rj is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R\ is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2 l -stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6- (N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid

disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, R\ is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4 l -bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy

Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.

OTHER INGREDIENTS A variety of other ingredients may be included in the compositions and processes of this invention, according to the desires of the formulator. The following are illustrative.

Detersive Surfactants - Nonlimiting examples of additional, non-amide surfactants useful herein include the conventional Cn-Cj alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10- 20 ^- sulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 )χ(CHOSθ3 " M + ) CH 3 and CH 3 (CH 2 )y(CHOSO3 ' M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation,

especially sodium, unsaturated sulfates such as oleyl sulfate, the Cjo- i alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), Cjo-Ci alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the CJO-18 gtycerol ethers, the Cio-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and Cj2-Ci8 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C12- 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-Ci2 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12- 18 betaines and sulfobetaines ("sultaines"), CjQ-Cig amine oxides, and the like, can also be included in the overall compositions. C10- 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Cig soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. If used, such additional surfactants typically comprise from about 1% to about 55% by weight of the compositions herein. Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front-loading 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 encompasses monocarboxylic fatty acis and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, I960 * 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 atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cjg-C4o ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate

esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40°C and about 50°C, and a minimum boiling point not less than about 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.

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

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

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25°C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (013)3 SiO 1/2 umts °f Siθ2 units in a ratio of from (CH3)3 SiOj/2 units and to S-O2 units of from about 0.6:1 to about 1.2:1; and

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

In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene- polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and not linear.

To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35. The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200 PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol: copolymer of polyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC LIOI.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2- alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones

disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the Cg-Cjg alkyl alcohols having a CJ-CJO chain. A preferred alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5 : 1.

For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.

The compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.

Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of paniculate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise

from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2Siθ5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x θ2χ+ yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiO5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid

detergent formulations. Aluminosilicate builders include those having the empirical formula:

M z (zAlO 2 )y] xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na 12 [(Alθ2)i2(SiO 2 ) 12 ] xH 2 O wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids

such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with aeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C 2 Q alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,

Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.

Fatty acids, e.g., Cj 2 -Cι monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- 1 - hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S.

Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite 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, paniculate soil release peptization, and anti-redeposition.

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 include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein 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 water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from 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 range from about 30: 1 to about 1:1, more preferably from about 10: 1 to 2: 1. Water- soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. Another polymeric material which can be included is polyethylene glycol

(PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes

range from about 500 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 polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.

Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration. The enzymes to be incorporated include proteases, amylases, Upases, cellulases, and peroxidases, 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 active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. 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 trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The 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 example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

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 in GB- 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 microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also Upases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This Upase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial Upases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and commercially avaUable from Novo (see also EPO 341,947) is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S. 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 detergents 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. Enzyme Stabilizers - The enzymes employed herein are typically stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium 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 to about 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 calcium 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 magnesium 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 magnesium salt can be used as the source of calcium or magnesium ions, including, but not Umited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts. A small amount of calcium ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula 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 magnesium 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 grease removal performance. If used for such purposes, the compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of

calcium or magnesium 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 3%, 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 preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium 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.

Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Bums et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6- nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bu s et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaUer than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or RlC(O)N(R 5 )R 2 C(O)L wherein } is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R $ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate. Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfo- nate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

wherein R^ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

Polymeric Soil Release Agent - 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 nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and,

thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

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) oxypropylene 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 oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile 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 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4- Cg alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are amphiphiUc, whereby they have a sufficient level of C1-C4 alkyl ether and or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include - cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end- capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.

Clay Soil Removal Anti-redeposition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates,

diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates 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. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.

EXPERIMENTAL Undesirable transfer of dyes from one fabric to another in consumer laundry can be determined as follows. White fabrics are laundered in the presence of a controlled amount of dyed fabric. The dyed fabric releases some dye into the wash water, and some of this fugitive dye is retained on the white fabrics. The amount of dye released and then retained is in part a function of the composition of the detergent solution.

Following this general procedure, individual surfactant solutions at concentrations of 160 ppm, 800 ppm and 1600 ppm in water are prepared for testing.

A non-phosphate builder system comprising 57 ppm zeolite A, 18 ppm sodium

citrate, 23 ppm citric acid, 83 ppm SKS-6 and 58 ppm acrylate/maleate polymer in water is used in the test solutions. The pH is around 9.8.

White cotton test swatches are placed into a simulated washing machine (Tergotometer) together with swatches of cloth which are designed to "bleed" dyes. Both DR80 (Direct Red 80) and AR151 (Acid Red 151) type bleeding swatches (Textile Innovators Corporation) are used. The surfactant/builder systems being tested are agitated with the white test swatches and the bleeding swatches for about 16 minutes. Temperature of the aqueous liquor is 95°F (35°C).

The extent of dye transfer in fabric laundering can be conveniently quantified using colorimetric instrumentation. The colorimeter is known as the MiniScan, Model No. MS/S4500L, made by Hunter Associates Laboratory, Inc., Reston, VA. This spectrophotometer uses a 45 illumination geometry with a 0 viewer, with a relatively large (25 millimeter diameter) observing window. A UV cut-off filter is attached to the spectrophotometer to prevent illumination of the sample by ultraviolet light (thereby eliminating the effect of fabric whitening agents). This spectrophotometer is calibrated to report the colorimetric units L, a, b according to the standard illuminant "C" and the 2 standard observer. Additional information describing the various colorimetric techniques may be found in ASTM Standards on Color and Appearance Measurement. Second Edition. ASTM, Philadelphia, PA 1987. Each fabric is read twice, recording the average of these two readings as L, a, b values. Each fabric is also read both before and after laundering. One convenient measure of the change in color is known as "delta E", calculated as follows: delta E = [(Lbefore-Lafter) 2 + (abefore- a after) 2 + (bbefore-bafter) 2 ]' 72 - Relatively small values of delta E are desirable in these tests, in that they describe reduced contamination of fabrics by the fugitive dyes. Representative data for several types of surfactants, including those showing the improved performance of the surfactants of the present invention (PFAA and ALKOXY PFAA), appear in Figure 1.

Preferred compositions herein provide minimal dye transfer between fabrics, i.e., a difference in delta E value as measured hereinabove vs. LAS control on cotton, of at least about 5, preferably a delta E difference of at least about 20.

The following illustrates a variety of detergent compositions in accordance with this invention, but is not intended to be limiting thereof.

EXAMPLE I A liquid laundry detergent composition comprises the following: Ingredient % (wt c 12-14 E0 2 - 25 sulfate 15.0 Cι 2 _i4 alkyl sulfate 6.0 12- 14-N-methyl glucamide 6.0

Sodium citrate 6.0

Monoethanolamine 2.5

Water/propylene glycol ethanol (100: 1 : 1) Balance In the above formulation, the glucamide surfactant can be replaced by an equivalent amount of the Cjo-Cj fatty acid amides of N-(3-methoxypropyl) glucamine to secure improved inhibition of dye transfer between fabrics.

EXAMPLE π A granular laundry detergent comprises the following: Ingredient % (wt

C 12 alkyl benzene sulfonate 12.0

C 16- 18-N-methyl glucamide 12.0

Zeolite A ( 1 - 10 micrometer) 26.0

^12-14 secondary (2,3) alkyl sulfate, Na salt 5.0 Sodium citrate 5.0

Sodium carbonate 20.0

Detersive enzyme* 1.0

Sodium sulfate 9.0

TINOPAL-UNPA-GX 0.1 Water and minors Balance

*Lipolytic enzyme preparation (LIPOLASE).

In the above formulation, the glucamide surfactant can be replaced by an equivalent amount of the corresponding Cι 2 _ιg fatty acid amides of N-(2- methoxyethyl) glucamine or N-(3-methoxypropyl) glucamine, respectively, to provide improved dye transfer inhibition.

EXAMPLE m A laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: Ingredient % (wt.) C12-I6 alky 1 sulfate, Na 20

Palm N-methyl glucamide* 5

C 11 - 13 alkyl benzene sulfonate, Na 10

Sodium tripolyphosphate 7

Sodium pyrophosphate 7

Sodium carbonate 25

Zeolite A (0.1-1 Oμ) 5

Coconut monoethanolamide 2

Carboxymethylcellulose 0.2

Polyacrylate (m.w. 1400) 0.2

Brightener, perfume 0.2

Protease enzyme 0.3

Cellulase enzyme** 0.2

CaSO4 1

MgSO 4 1

PVNO (mol. wt. 50,000) 0.5

Water 4

Filler*** Balance

*Prepared from mixed palm fraction fatty acids.

**As CAREZYME (Novo).

***Can be selected from convenient materials such as CaCO3, talc, clay, silicates, and the like.

EXAMPLE IV

A granular laundry detergent comprises the following ingredients:

Ingredient % (wt

Coconutalkyl sulfate 1 7.0

Coconut EO(3) sulfate 1.7

Cl2-14 EO(5) 6.0 l2-14 N-methyl glucamide 2 2.6

Suds control 3 0.8

ZeoUte A 18.0

Citrate 4.5

Citric Acid 1.8

Layered silicate 4 6.5

PVNO/PVPVI 5 0.1

Enzymes * 1.5

Sodium carbonate 3.7

Sodium bicarbonate 3.7

Sodium sulfate/moisture/perfume/minors Balance May be replaced by tallowalkyl sulfate for high temperature wash.

2 May range from 2.0% to 3.0%, by weight, of finished composition. 3 Mixture of HYFAC/silicone. 4 As SKS-6, ex. Hoechst. 5 Weight ratio of 3:1 to 1:3 may be used. 6 Mixture of ALCALASE, LIPOLASE, CAREZYME, TERMAMYL and ENDOLASE, all from commercial sources.