WO2000047706A1

WO2000047706A1 - Methods for reducing damage to laundered fabrics

Info

Publication number: WO2000047706A1
Application number: PCT/US2000/003518
Authority: WO
Inventors: Mary Vijayarani Barnabas; Toan Trinh
Original assignee: The Procter & Gamble Company
Priority date: 1999-02-10
Filing date: 2000-02-09
Publication date: 2000-08-17
Also published as: AU3999400A

Abstract

This invention relates to surfactant-containing laundry detergent products and methods for using such products to reduce damage to fabrics that go through many wash then wear cycles ('wash and wear fabrics'), especially fabrics made from cellulosic fibers, such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof, compared to laundry detergent products with low organic surfactants.

Description

METHODS FOR REDUCING DAMAGE TO LAUNDERED FABRICS

FIELD OF THE INVENTION

This invention relates to surfactant-containing laundry detergent products and methods for using such products to reduce damage to fabrics that go through many wash then wear cycles ("wash and wear fabrics"), especially fabrics made from cellulosic fibers, such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel ®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof, compared to laundry detergent products with low organic surfactant content and/or alternative laundry products that do not contain surfactants.

BACKGROUND OF THE INVENTION

There is a continuous need for textile technologists to produce laundry detergent compositions and products that provide useful value-added benefits, besides cleaning, to fabrics, especially clothing, such as maintaining fabric condition, e.g., strength and/or size, and reducing fabric wear. There is also economic pressures that demand low cost

"value brand" detergent compositions and products. Most low cost detergent products consist of compositions containing .low levels of organic surfactants and high levels of materials that provide a high alkalinity to the wash water, such as soluble silicates and/or carbonates. Other recent alternative laundry products bypass the organic surfactants altogether, and depend on materials such as magnets and/or discs of activated ceramic particles. The above alternative laundry products can normally reused many times, and claim great saving for the consumers. Consumer garments are subjected to multiple wash cycles during the effective lifetime of the fabrics. In each wash cycle, the fibers in garments go through a tremendous amount of stress and strain. During a wear cycle, the garments are again exposed to many mechanical abrasion due to the normal activities of the wearer. Multiple cycles of wash and wear process result in several visual effects including appearance loss, dye loss, wrinkles, shrinkage, fiber/fabric damage (often times visible, but also can be measured as weight loss of fabric) or strength loss, etc. Both natural (e.g., cotton) and regenerated (e.g., Rayon, Lyocell) fibers are affected by the wash and wear process. The extent of damage depends on the wash and wear conditions, wash process and the products used in the wash. Natural fibers have unevenly distributed defects that are more susceptible or prone to attack, by for example, bleach, friction or abrasion. Regenerated fibers, such as Rayon, have uniform fibers with amorphous regions spread out mainly on the surface of the fiber. The magnitude of the fiber-damage varies for different type of fibers.

There are two main types of damage that fibers and fabrics can undergo during the wash and wear process. The first type of damage is mechanical abrasion/friction damage producing fuzz and pill and fiber breakage. Mechanical damage causes a decrease in the abrasion resistance of the fabrics. The second type of damage is chemical damage, such as bleach damage (i.e., oxidative damage). Oxidative damage is reflected by an increase of carbonyl groups and aldehyde groups on the fabric surface. The two types of damage are interdependent in that one type of damage will make the fabric more prone to the other type. Thus the abrasion resistance of a fabric is decreased when it is soaked in a higher level of hypochlorite bleach and/or at longer soaking time.

It is now found surprisingly that laundry detergent compositions with high contents of organic surfactants, do not damage or significantly reduce the fabric damage resulting from the multiple wash and wear cycles, as compared to laundry compositions with low contents of organic surfactants and/or laundry products that do not contain organic surfactants such as laundry discs (A.C. Lumley, B.M. Gatewood, "Effectiveness of Selected Laundry Disks in Removing Soil and Stains from Cotton and Polyester", Textile Chemist and Colorist, December 1998, pp. 31-35) commercially available under the trade name CLEAN POWER PLUS from The Magellan Group of Chattanooga, Tennessee, balls and other non-surfactant containing "cleaning" objects and/or devices. Therefore, there is a need to incorporate instructions for use to laundry products containing high levels of organic surfactants to direct the consumers to use the composition at a suitable level to provide the benefit that fabric damage is not damaged or the damage is reduced as compared to a comparable treatment with lower levels of, or no, organic surfactants. The benefit is especially obtained for cellulosic fibers, such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel ®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof. It is surprisingly found that even after 25 cycles of wash using a suitably high level of organic surfactant, under relatively harsh conditions, the integrity of cotton fabrics is not affected very much. The integrity of the fabrics is measured in terms of bleach damage, i.e., the extent of carboxyl groups and/or aldehyde groups on surface, and abrasion damage in terms of fiber weight loss in wet abrasion. Physical parameters, such as relative crystallinity and moisture regain change to a measurable extent when fabrics are washed without detergents, but the they are not altered much when washed with detergents.

SUMMARY OF THE INVENTION

The present invention relates to an article of manufacture comprising a granular, paste, gel or liquid laundry detergent composition comprising a high level of a surfactant system including one or more surfactants packaged in a container in association with instructions to use the composition at a level that will provide from about 100 ppm to about 2500 ppm, preferably from about 300 ppm to about 1800 ppm, of organic surfactant in the aqueous wash solution to provide the benefit that fabric damage is reduced as compared to a comparable treatment with lower level of, or no, surfactants. In one aspect of the present invention, an article of manufacture comprising a granular, paste, gel or liquid laundry detergent composition comprising a high level of a surfactant system including one or more surfactants packaged in a container in association with instructions to use the composition is provided. In another aspect of the present invention, a method for reducing fabric damage to fabric that is subjected to multiple wash cycles is provided.

These and other aspects, objects, features and advantages will be clear from the following detailed description, examples and appended claims. All percentages, ratios and proportions herein are on a weight basis unless otherwise indicated. All documents cited herein are hereby incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an article of manufacture comprising a granular, paste, gel or liquid laundry detergent composition comprising a high level of a surfactant system including one or more surfactants packaged in a container in association with instructions to use the composition at a level that will provide a level of organic surfactant of from about 100 ppm to about 2500 ppm, preferably from about 300 ppm to about 1800 ppm, by weight of the aqueous wash solution, to provide the benefit that fabric damage is reduced as compared to a comparable treatment with lower level of, or no, surfactants. The preferred levels of organic surfactant vary with the type of washing machines used. For horizontal axis washing machines, the preferred level of surfactant is from about 800 ppm to about 2500 ppm, more preferably from about 900 ppm to about 1700 ppm, by weight of the aqueous wash solution. For vertical axis washing machines, the preferred level of surfactant is from about 200 ppm to about 1000 ppm, more preferably from about 300 ppm to about 900 ppm, by weight of the aqueous wash solution. For twin-tub washing machines, the preferred level of surfactant is from about 100 ppm to about 300 ppm, by weight of the aqueous wash solution.

It has been found that high levels of surfactant in laundry detergent compositions result in the lubrication of the fibers of the fabrics being cleaned. Without wishing to be bound by theory, it is believed that by sufficiently lubricating the fibers of a fabric being washed, damage by abrasion as a result of fiber-to-fiber contact and/or fiber-to-non-fiber contact is reduced or prevented.

Further, it has been found that high levels of surfactant in laundry detergent compositions protect fabrics from bleach damage. Without wishing to be bound by theory, it is believed that by coating the fibers of a fabric with a high level of surfactant, the surfactant protects the fabric from bleach damage. Bleach can typically oxidatively damage the fabric, however, it is believed that the surfactant coats the fabric in such a way that the bleach attacks the surfactant rather than the fabric. METHODS FOR REDUCING FABRIC DAMAGE

A method for reducing fabric damage to wash and wear fabric that is subjected to multiple wash cycles, the method comprising contacting said fabric with a treating composition comprising a surfactant system including one or more surfactants such that the fabric damage of said treated fabric is less than the fabric damage to a fabric that is not treated with a surfactant system. Especially preferred surfactants include long chain alkyl surfactants.

Preferably, the treating composition further comprises additional cleaning adjunct materials selected from the group consisting of bleaching agents, builders, alkalinity sources and mixtures thereof. Preferably, the treating composition further comprises additional cleaning adjunct materials selected from the group consisting of enzymes, chelants, soil releasing agents, dye transfer inhibiting agents, fabric softening agents, and other conventional detergent ingredients.

Preferably, the surfactant is present in said treating composition at a level such that from about 100 ppm to about 2500 ppm of surfactant is present in a wash solution comprising said treating composition.

Under wash conditions using twin-tub washing machines, such as Japanese washing machines, it is preferable that the surfactant is present at a level of from about 100 ppm to about 300 ppm in a wash solution comprising said treating composition. Under wash conditions using vertical axis washing machines, such as North

American washing machines, it is preferable that the surfactant is present at a level of from about 200 ppm to about 1000 ppm, more preferably from about 300 ppm to about 900 ppm in a wash solution comprising said treating composition.

Under wash conditions using the horizontal axis washing machines, such as European washing machines, it is preferable that the surfactant is present at a level of from about 800 ppm to about 2500 ppm, more preferably from about 900 ppm to about 1700 ppm in a wash solution comprising said treating composition.

The fabric is preferably made from natural fibers. Preferably, the fabric is made from cellulosic fibers, such as cotton, rayon, ramie, jute, flax, linen, polynosic-fibers, Lyocell (Tencel ®), polyester/cotton blends, other cotton blends, and the like, especially cotton, rayon, linen, polyester/cotton blends, and mixtures thereof. TEST PROTOCOLS

Oxidative Damage (Bleach Damage) was measured by determining the carboxyl groups and aldehyde groups on the fabric surface. Carboxyl groups were measured using ATR and Turnbull's blue test. Aldehyde groups were measured using Fehling's Solution test.

Abrasion Resistance of the fabric and Pilling Resistance of the fabric was measured using a Martindale abrader, preferably a Nu-Martindale Abrasion and Pilling Tester. I. Wet Abrasion Resistance Method - Wet abrasion resistance is measured in terms of fabric weight loss after a certain number of abrasion cycles under pressure wherein the fabric being tested is in contact with a thicker fabric, such as wool. Increasing wet abrasion cycles (in Martindale abrader) results in increased fiber weight loss. No additional carboxyl groups are produced by just abrasion cycles. (In fact, carboxyl containing fibers on surface may be removed due to abrasion).

LI. Pilling Resistance Method - Pilling resistance is measured in terms of appearance of the fabric being tested. This method is typically performed to measure the early cycle effects. In this method, the fabric being tested is in contact with another piece of the same type of fabric. Also, under this method, the two fabrics are in contact with one another without any additional pressure being added, unlike the Wet Abrasion Resistance Method.

SURFACTANT-CONTAINING LAUNDRY DETERGENT PRODUCTS

The laundry detergent compositions in accordance with the present invention comprise one or more surfactants, preferably long chain alkyl surfactants and/or surfactants that adhere to the fabric, and preferably one or more additional cleaning adjuncts, preferably compatible with the surfactant(s). The term "cleaning adjunct materials", as used herein, means any liquid, solid or gaseous material selected for the particular type of laundry composition desired and the form of the product (e.g., liquid; granule; powder; gel composition), which materials are also preferably compatible with the surfactants.

The specific selection of cleaning adjunct materials are readily made by considering the surface, item or fabric to be cleaned, and the desired form of the composition for the laundry conditions during use (e.g., through the wash detergent use). The term "compatible", as used herein, means the cleaning adjunct materials do not reduce the detersive activity of the other detergent ingredients, especially the enzymes. Examples of suitable cleaning adjunct materials include, but are not limited to, surfactants, builders, bleaches, bleach activators, bleach catalysts, other enzymes, enzyme stabilizing systems, chelants, optical brighteners, soil release polymers, dye transfer agents, dispersants, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, color speckles, silvercare, anti-tarnish and/or anti-corrosion agents, alkalinity sources, solubilizing agents, carriers, processing aids, pigments and pH control agents as described in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101. Specific cleaning adjunct materials are exemplified in detail hereinafter.

When the laundry compositions of the present invention are formulated as compositions suitable for use in a laundry machine washing method, the compositions of the present invention preferably contain both a surfactant and a builder compound and additionally one or more cleaning adjunct materials preferably selected from organic polymeric compounds, bleaching agents, additional enzymes, suds suppressers, dispersants, lime-soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also contain softening agents, as additional cleaning adjunct materials. The compositions of the present invention can also be used as detergent additive products in solid or liquid form. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and can be added at any stage of the laundry process. If needed the density of the laundry detergent compositions herein ranges from

400 to 1200 g/litre, preferably 500 to 950 g/litre of composition measured at 20°C.

The "compact" form of the laundry compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In the compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.

Liquid laundry compositions according to the present invention can also be in a "concentrated form", in such case, the liquid laundry compositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents. Typically the water content of the concentrated liquid laundry composition is preferably less than 40%, more preferably less than 30%, most preferably less than 20% by weight of the laundry composition.

The laundry detergent compositions and/or products preferably incorporate low density filler particles of the present invention in an amount sufficient to suspend the particulate solids of the present invention such that the laundry detergent compositions and/or products of the present invention are similar in properties to laundry detergent compositions and/or products comprising particulate solids having a particle density of from about 0.8 to about 2.1 g/mL, more preferably from about 0.8 to about 1.5 g/mL, most preferably from about 0.9 to about 1.2 g/mL. CLEANING ADJUNCT MATERIALS The laundry detergent compositions of the present invention as described hereinbefore may optionally include, in addition to the particulate solids of the present invention, cleaning adjunct materials described below. Biodegradably branched surfactants The present invention includes important embodiments comprising at least one biodegradably branched and/or crystallinity disrupted and/or mid-chain branched surfactant or surfactant mixture. The terms "biodegradably branched" and/or "crystallinity disrupted" and/or "mid-chain branched" (acronym "MCB" used hereinafter) indicate that such surfactants or surfactant mixtures are characterized by the presence of surfactant molecules having a moderately non-linear hydrophobe; more particularly, wherein the surfactant hydrophobe is not completely linear, on one hand, nor is it branched to an extent that would result in unacceptable biodegradation. The preferred biodegradably branched surfactants are distinct from the known commercial LAS, ABS, Exxal, Lial, etc. types, whether branched or unbranched. The biodegradably branched materials comprise particularly positioned light branching, for example from about one to about three methyl, and/or ethyl, and/or propyl or and/or butyl branches in the hydrophobe, wherein the branching is located remotely from the surfactant headgroup, preferably toward the middle of the hydrophobe. Typically from one to three such branches can be present on a single hydrophobe, preferably only one. Such biodegradably branched surfactants can have exclusively linear aliphatic hydrophobes, or the hydrophobes can include cycloaliphatic or aromatic substitution. Highly preferred are MCB analogs of common linear alkyl sulfate, linear alkyl poly(alkoxylate) and linear alkylbenzenesulfonate surfactants, said surfactant suitably being selected from mid-chain-Cι-C₄-branched C₈- Cι₈-alkyl sulfates, mid-chain-Ci-C₄-branched C₈-Cι₈-alkyl ethoxylated, propoxylated or butoxylated alcohols, mid-chain-Cι-C -branched C₈-Cι₈-alkyl ethoxysulfates, mid-chain- Cι-C₄-branched C₈-Cι₆-alkyl benzenesulfonates and mixtures thereof. When anionic, the surfactants can in general be in acid or salt, for example sodium, potassium, ammonium or substituted ammonium, form. The biodegradably branched surfactants offer substantial improvements in cleaning performance and/or usefulness in cold water and/or resistance to water hardness and/or economy of utilization. Such surfactants can, in general, belong to any known class of surfactants, e.g., anionic, nonionic, cationic, or zwitterionic. The biodegradably branched surfactants are synthesized through processes of Procter & Gamble, Shell, and Sasol. These surfactants are more fully disclosed in WO98/23712 A published 06/04/98; WO97/38957 A published 10/23/97; WO97/38956 A published 10/23/97; WO97/39091 A published 10/23/97; WO97/39089 A published 10/23/97; WO97/39088 A published 10/23/97; WO97/39087 Al published 10/23/97; WO97/38972 A published 10/23/97; WO 98/23566 A Shell, published 06/04/98; technical bulletins of Sasol; and the following pending patent applications assigned to Procter & Gamble:

Preferred biodegradably branched surfactants herein in more detail include MCB surfactants as disclosed in the following references: WO98/23712 A published 06/04/98 includes disclosure of MCB nonionic surfactants including MCB primary alkyl polyoxyalkylenes of formula (1): CH₃CH₂(CH₂)_wC(R)H(CH₂)_xC(R¹)H(CH₂)_yC(R²)H(CH₂)_z(EO/PO)_mOH (1), where the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, R¹ and R² branching, but not including the carbon atoms in the EO/PO alkoxy moiety, is preferably 14-20, and wherein further for this surfactant mixture, the average total number of carbon atoms in the MCB primary alkyl hydrophobe moiety is preferably 14.5-17.5, more preferably 15-17; R, R¹ and R² are each independently selected from hydrogen and 1-3C alkyl, preferably methyl, provided R, R¹ and R² are not all hydrogen and, when z is 1, at least R or R¹ is not hydrogen; w is an integer of 0-13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1; w+x+y+z is 8-14; and EO/PO are alkoxy moieties preferably selected from ethoxy, propoxy and mixed ethoxy/propoxy groups, where m is at least 1, preferably 3-30, more preferably 5-20, most preferably 5-15. Such MCB nonionics can alternately include butylene oxide derived moieties, and the -OH moiety can be replaced by any of the well-known end-capping moieties used for conventional nonionic surfactants.

WO97/38957 A published 10/23/97 includes disclosure of mid- to near-mid-chain branched alcohols of formulae R-CH₂CH₂CH(Me)CH-R'-CH₂OH (I) and HOCH₂-R- CH₂-CH₂-CH(Me)-R' (LT) comprising: (A) dimerising alpha -olefins of formula RCH=CH₂ and R'CH=CH₂ to form olefins of formula R(CH₂)₂-C(R¹)=CH₂ and R^l(CH₂)₂-C(R)=CH₂; (B) (i) isomerising the olefins and then reacting them with carbon monoxide/hydrogen under Oxo conditions or (ii) directly reacting the olefins from step (A) with CO/H₂ under Oxo conditions. In the above formulae, R, R¹ = 3-7C linear alkyl. WO97/38957 A also discloses (i) production of MCB alkyl sulfatesulfat surfactants by sulfatingsulfat (I) or (II); (ii) preparation of MCB alkylethoxy sulfatessulfat which comprises ethoxylating and then sulfating (I) or (II); (iii) preparation of MCB alkyl carboxylate surfactants which comprises oxidizing (I) or (II) or their aldehyde intermediates and (iv) preparation of MCB acyl taurate, MCB acyl isethionate, MCB acyl sarcosinate or MCB acyl N-methylglucamide surfactants using the branched alkyl carboxylates as feedstock.

WO97/38956 A published 10/23/97 discloses the preparation of mid- to near mid- chain branched alpha olefins which is effected by: (a) preparing a mixture of carbon monoxide and hydrogen; (b) reacting this mixture in the presence of a catalyst under Fischer-Tropsch conditions to prepare a hydrocarbon mixture comprising the described olefins; and (c) separating the olefins from the hydrocarbon mixture. WO97/38956 A further discloses the preparation of mid- to near mid-chain branched alcohols by reacting the olefins described with CO/H₂ under Oxo conditions. These alcohols can be used to prepare (1) MCB sulfate surfactants by sulfating the alcohols; (2) MCB alkyl ethoxy sulfates by ethoxylating, then sulfating, the alcohols; or (3) branched alkyl carboxylate surfactants by oxidizing the alcohols or their aldehyde intermediates. The branched carboxylates formed can be used as a feedstock to prepare branched acyl taurate, acyl isethionate, acyl sarcosinate or acyl N-methylglucamide surfactants, etc.

WO97/39091 A published 10/23/97 includes disclosure of a detergent surfactant composition comprising at least 0.5 ( especially 5, more especially 10, most especially 20) wt% of longer alkyl chain, MCB surfactant of formula (I). A-X-B (1) wherein A is a 9-22 (especially 12-18) C MCB alkyl hydrophobe having: (i) a longest linear C chain attached to the X-B moiety of 8-21 C atoms; (ii) 1-3C alkyl moiety(s) branching from this longest linear chain; (iii) at least one of the branching alkyl moieties attached directly to a C of the longest linear C chain at a position within the range of position 2 C, counting from C 1 which is attached to the CH₂B moiety, to the omega-2 carbon (the terminal C minus 2C); and (iv) the surfactant composition has an average total number of C atoms in the A-X moiety of 14.5-17.5 ( especially 15-17); and B is a hydrophilic (surfactant head-group) moiety preferably selected from sulfates, sulfonates, polyoxyalkylene ( especially polyoxyethylene or polyoxypropylene), alkoxylated sulfates, polyhydroxy moieties, phosphate esters, glycerol sulphonates, polygluconates, polyphosphate esters, phosphonates, sulphosuccinates, sulphosuccinates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, mono-/di-alkanol-amides, monoalkanolamide sulfates, diglycol-amide and their sulfates, glyceryl esters and their sulfates, glycerol ethers and their sulfates, polyglycerol ether and their sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonio-alkane-sulphonates, amidopropyl betaines, alkylated quat., alkylated/poly-hydroxyalkylated (oxypropyl) quat., imidazolines, 2-yl succinates, sulphonated alkyl esters and sulphonated fatty acids; and X- is -CH₂- or - C(O)-. WO97/39091 A also discloses a laundry detergent or other cleaning composition comprising: (a) 0.001-99% of detergent surfactant (I); and (b) 1 - 99.999% of adjunct ingredients.

WO97/39089 A published 10/23/97 includes disclosure of liquid cleaning compositions comprising: (a) as part of surfactant system 0.1-50 (especially 1-40) wt % of a mid-chain branched surfactant of formula (I); (b) as the other part of the surfactant system 0.1-50 t% of co-surfactant(s); (c) 1-99.7 wt% of a solvent; and (d) 0.1-75 wt% of adjunct ingredients. Formula (I) is A-CH -B wherein A = 9-22 (especially 12-18) C MCB alkyl hydrophobe having: (i) a longest linear C chain attached to the X-B moiety of 8-21 C atoms; (ii) 1-3C alkyl moiety(s) branching from this longest linear chain; (iii) at least one of the branching alkyl moieties attached directly to a C of the longest linear C chain at a position within the range of position 2 C, counting from Carbon No. 1 which is attached to the CH B moiety, to the omega-2 carbon (the terminal C minus 2C); and (iv) the surfactant composition has an average total number of C atoms in the A-X moiety of 14.5-17.5 ( especially 15-17); and B is a hydrophilic moiety selected from sulfates, polyoxyalkylene (especially polyoxyethylene and polyoxypropylene) and alkoxylated sulfates.

WO97/39088 A published 10/23/97 includes disclosure of a surfactant composition comprising 0.001-100% of MCB primary alkyl alkoxylated sulfate(s) of formula (I): CH₃CH₂(CH)_wCHR(CH₂)_xCHR¹(CH₂)_yCHR²(CH₂)_zOSO₃M (I) wherein the total number of C atoms in compound (I) including R, R and R , is preferably 14-20 and the total number of C atoms in the branched alkyl moieties preferably averages 14.5-17.5 (especially 15-17); R, R¹ and R² are selected from H and 1-3C alkyl ( especially Me) provided R, R¹ and R² are not all H; when z = 1 at least R or R¹ is not H; M are cations especially selected from Na, K, Ca, Mg, quaternary alkyl ammonium of formula N⁺R³R⁴R⁵R⁶ (II); M is especially Na and/or K; R³, R⁴, R⁵, R⁶ are selected from H, 1-22C alkylene, 4-22C branched alkylene, 1-6C alkanol, 1-22C alkenylene, and/or 4-22C branched alkenylene; w, x, y = 0-13; z is at least 1 ; w+x+y+z = 8-14. WO97/39088 A also discloses (1) a surfactant composition comprising a mixture of branched primary alkyl sulfates of formula (I) as above. M is a water-soluble cation; When R² is 1-3C alkyl, the ratio of surfactants having z = 1 to surfactants having z = 2 or greater is preferably at least 1 :1 ( most especially 1 :100); (2) a detergent composition comprising: (a) 0.001-99% of MCB primary alkyl alkoxylated sulfate of formula (LT) and/or (TV). CH₃(CH₂)_aCH(CH₃)(CH₂)_bCH₂OSO₃M (m) CH₃(CH₂)_dCH(CH₃)(CH₂)eCH(CH₃)CH₂OSO₃M (IV) wherein a, b, d, and e are integers, preferably a+b = 10-16, d+e = 8-14 and when a+b = 10, a - 2-9 and b = 1-8; when a+b = l l, a = 2-10 and b = 1-9; when a+b = 12, a - 2-11 and b = 1-10; when a+b - 13, a = 2-12 and b = 1-11 ; when a+b = 14, a = 2-13 and b = 1-12; when a+B = 15, a = 2-14 and b = 1- 13; when a+b = 16, a = 2-14 and b = 1-14; when d+e = 8, d = 2-7 and e = 1-6; when d+e = 9, d = 2-8 and e = 1-7; when d+e = 10, d = 2-9 and e = 1-8; when d+e = 11, d = 2-10 and e = 1-9; when d+e = 12, d = 2-11 and e = 1-10; when d+e = 13, d = 2-12 and e = 1-11; when d+e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99 t% of detergent adjuncts; (3) a mid-chain branched primary alkyl sulfate surfactant of formula(V): CH₃CH₂(CH₂)_xCHR¹(CH₂)_yCHR²(CH₂)_zOSO₃M (V) wherein x, y = 0-12; z is at least 2; x+y+z = 11-14; R¹ and R² are not both H; when one of R¹ or R² is H, and the other is Me, x + y +z is not 12 or 13; and when R¹ is H and R² is Me, x + y is not 11 when z = 3 and x + y is not 9 when z = 5; (4) Alkyl sulfates of formula (in) in which a and b are integers and a = b = 12 or 13, a = 2-11, b = 1-10 and M is Na, K, and optionally substituted ammonium; (5) alkyl sulfates of formula (IN) in which d and e are integers and d = e is 10 or 11 and when d = e is 10, d = 2-9 and e = 1-8; when d = e = l l, d = 2-10 and e = 1-9 and m is Νa, K, optionally substituted ammonium ( especially Νa); (6) methyl branched primary alkyl sulfates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12- or 13- methyl pentadecanol sulfate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12-, 13-, or 14- methyl hexadecanol sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12-methyl tetradecanol sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,1 1-, 2,12-, or 2,13- methyl pentadecanol sulfate and/or mixtures of these compounds. WO97/39087 A published 10/23/97 includes disclosure of a surfactant composition comprising 0.001-100% of mid-chain branched primary alkyl alkoxylated sulfate(s) of formula (I) wherein that total number of C atoms in compound (I) including R, R¹ and R³, but not including C atoms of EO/PO alkoxy moieties is 14-20 and the total number of C atoms in branched alkyl moieties averages 14.5-17.5 (especially 15-17); R, Rl and R2 = H or 1-3C alkyl ( especially Me) and R, R¹ and R² are not all H; when z = 1 at least R or R¹ is not H; M = cations especially selected from Na, K, Ca, Mg, quaternary alkyl amines of formula (II) ( M is especially Na and/or K) R³, R⁴, R⁵, R⁶ = H, 1-22C alkylene, 4-22C branched alkylene, 1-6C alkanol, 1-22C alkenylene, and/or 4-22C branched alkenylene; w, x, y = 0-13; z is at least 1; w+x+y+z = 8-14; EO/PO are alkoxy moieties, especially ethoxy and/or propoxy; m is at least 0.01, especially 0.1-30, more especially 0.5-10, most especially 1-5. Also disclosed are: (1) a surfactant composition comprising a mixture of branched primary alkyl alkoxylated sulfates of formula (I) When R² = 1-3C alkyl, the ratio of surfactants having z = 2 or greater to surfactant having z = 1 is at least 1 :1, especially 1.5:1, more especially 3:1, most especially 4:1; (2) a detergent composition comprising: (a) 0.001-99%) of mid-chain branched primary alkyl alkoxylated sulfate of formula (Lπ) and/or (IN) M is as above; a, b, d, and e are integers, a+b = 10-16, d+e = 8-14 and when a+b = 10, a = 2-9 and b = 1-8; when a+b = 11, a = 2-10 and b = 1-9; when a+b = 12, a = 2-11 and b = 1-10; when a+b = 13, a = 2-12 and b = 1-11; when a+b = 14, a = 2-13 and b = 1-12; when a+b = 15, a = 2-14 and b = 1-13; when a+b = 16, a = 2- 14 and b = 1-14; when d+e = 8, d = 2-7 and e = 1-6; when d+e = 9, d = 2-8 and e = 1-7; when d+e = 10, d = 2-9 and e = 1-8; when d+e = 11, d = 2-10 and e = 1-9; when d+e = 12, d = 2-11 and e = 1-10; when d+e = 13, d = 2-12 and e = 1-11; when d+e = 14, d = 2-13 and e = 1-12; and (b) 1-99.99 wt% of detergent adjuncts; (3) a MCB primary alkyl alkoxylated sulfate surfactant of formula(V) Rl, R2, M, EO/PO, m as above; x,y = 0-12; z is at least 2; x+y+z = 11-14; (4) a mid-chain branched alkyl alkoxylated sulfate of formula (m) in which: a = 2-11; b = 1-10; a+b = 12 or 13; M, EO/PO and m are as above; (5) a mid-chain branched alkyl alkoxylated sulfate compound of formula (IN) in which: d+e = 10 or 1 1 ; when d+e = 10, d = 2-9 and e = 1-8 and when d+e = 11, d = 2-10 and e = 1-9; M is as above ( especially Νa); EO/PO and m are as above; and (6) methyl branched primary alkyl ethoxylated sulfates selected from 3-, 4- 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12- or 13- methyl pentadecanol ethoxylated sulfate; 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1 1-, 12-, 13-, or 14- methyl hexadecanol ethoxylated sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12- methyl tetradecanol ethoxylated sulfate; 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 2,9-, 2,10-, 2,11-, 2,12-, or 2,13- methyl pentadecanol ethoxylated sulfate and/or mixtures of these compounds. The compounds are ethoxylated with average degree of ethoxylation of 0.1- 10.

WO97/38972 A published 10/23/97 includes disclosure of a method for manufacturing longer chain alkyl sulfate surfactant mixture compositions comprising (a) sulfating with SO , preferably in a falling film reactor, a long chain aliphatic alcohol mixture having an average carbon chain length of at least 14.5-17.5, the alcohol mixture comprising at least 10%, preferably at least 25%>, more preferably at least 50% still more preferably at least 75%), most preferably at least 95% of a MCB aliphatic alcohol having formula (I); where: R,R',R² = H or 1-3C alkyl, preferably methyl, provided R, R¹ and R² are not all H, and when z = 1, at least R or R¹ is not H; w,x,y = integers 0-13; z = integer of at least 1; and w+x+y+z = 8-14; where the total number of carbon atoms in the branched primary, alkyl moiety of formula (I), including the R, R¹ and R² branching, is 14-20, and where further for the alcohol mixture the average total number of carbon atoms in the branched primary alkyl moieties having formula (I) is > 14.5-17.5, preferably, >15-17; and (b) neutralising the alkyl sulfate acid produced by step (a), preferably using a base selected from KOH, ΝaOH, ammonia, monoefhanolamine, triethanolamine and mixtures of these. Also disclosed is a method for manufacturing longer chain alkyl alkoxylated sulfate surfactant mixture compositions, comprising alkoxylating the specified long chain aliphatic alcohol mixture; sulfating the resulting polyoxyalkylene alcohol with SO₃; and neutralising the resulting alkyl alkoxylate sulfate acid. Alternatively, the alkyl alkoxylated sulfates may be produced directly from the polyoxyalkylene alcohol by sulfating with SO and neutralising. WO 98/23566 A Shell, published 06/04/98 discloses branched primary alcohol compositions having 8-36 C atoms and an average number of branches per mol of 0.7-3 and comprising ethyl and methyl branches. Also disclosed are: (1) a branched primary alkoxylate composition preparable by reacting a branched primary alcohol composition as above with an oxirane compound; (2) a branched primary alcohol sulfate preparable by sulfating a primary alcohol composition as above; (3) a branched alkoxylated primary alcohol sulfate preparable by alkoxylating and sulfating a branched alcohol composition as above; (4) a branched primary alcohol carboxylate preparable by oxidising a branched primary alcohol composition as above; (5) a detergent composition comprising: (a) surfactant(s) selected from branched primary alcohol alkoxylates as in (1), branched primary alcohol sulfates as in (2), and branched alkoxylated primary alcohol sulfates as in (3); (b) a builder; and (c) optionally additive(s) selected from foam control agents, enzymes, bleaching agents, bleach activators, optical brighteners, co-builders, hydrotropes and stabilisers. The primary alcohol composition, and the sulfates, alkoxylates, alkoxy sulfates and carboxylates prepared from them exhibit good cold water detergency and biodegradability.

Biodegradably branched surfactants useful herein also include the modified alkylaromatic, especially modified alkylbenzenesulfonate surfactants described in copending commonly assigned patent applications (P&G Case Nos. 7303P, 7304P). In more detail, these surfactants include (P&G Case 6766P) alkylarylsulfonate surfactant systems comprising from about 10%> to about 100% by weight of said surfactant system of two or more crystallinity-disrupted alkylarylsulfonate surfactants of formula (B-Ar-

D)a(M^cl⁺)b wherein D is SO3", M is a cation or cation mixture, q is the valence of said cation, a and b are numbers selected such that said composition is electroneutral; Ar is selected from benzene, toluene, and combinations thereof; and B comprises the sum of at least one primary hydrocarbyl moiety containing from 5 to 20 carbon atoms and one or more crystallinity-disrupting moieties wherein said crystallinity-disrupting moieties interrupt or branch from said hydrocarbyl moiety; and wherein said alkylarylsulfonate surfactant system has crystallinity disruption to the extent that its Sodium Critical Solubility Temperature, as measured by the CST Test, is no more than about 40°C and wherein further said alkylarylsulfonate surfactant system has at least one of the following properties: percentage biodegradation, as measured by the modified SCAS test, that exceeds tetrapropylene benzene sulfonate; and weight ratio of nonquaternary to quaternary carbon atoms in B of at least about 5:1.

Such compositions also include (P&G Case 7303P) surfactant mixtures comprising (preferably, consisting essentially of): (a) from about 60% to about 95% by weight (preferably from about 65% to about 90%, more preferably from about 70% to about 85%o) of a mixture of branched alkylbenzenesulfonates having formula (I):

(i) wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and having two methyl termini, and wherein said mixture of branched alkylbenzenesulfonates contains two or more (preferably at least three, optionally more) of said compounds differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzenesulfonates is characterized by an average carbon content of from about 10.0 to about 14.0 carbon atoms (preferably from about 11.0 to about 13.0, more preferably from about 11.5 to about 12.5), wherein said average carbon content is based on the sum of carbon atoms in R , L and R , (preferably said sum of carbon atoms in R , L and R² is from 9 to 15, more preferably, 10 to 14) and further, wherein L has no substituents other than A, R¹ and R²; M is a cation or cation mixture (preferably selected from H, Na, K, Ca, Mg and mixtures thereof, more preferably selected from H, Na, K and mixtures thereof, more preferably still, selected from H, Na, and mixtures thereof) having a valence q (typically from 1 to 2, preferably 1); a and b are integers selected such that said compounds are electroneutral (a is typically from 1 to 2, preferably 1, b is 1); R¹ is Cι-C₃ alkyl (preferably Cι-C₂ alkyl, more preferably methyl); R² is selected from H and Cι-C₃ alkyl (preferably H and C₁-C₂ alkyl, more preferably H and methyl, more preferably H and methyl provided that in at least about 0.5, more preferably 0.7, more preferably 0.9 to 1.0 mole fraction of said branched alkylbenzenesulfonates R is H); A is a benzene moiety (typically A is the moiety -C₆H₄- , with the SO₃ moiety of Formula (I) in para- position to the L moiety, though in some proportion, usually no more than about 5%, preferably from 0 to 5% by weight, the SO moiety is ortho- to L); and (b) from about 5% to about 60%) by weight (preferably from about 10% to about 35%, more preferably from about 15% to about 30%>) of a mixture of no nb ranched alkylbenzenesulfonates having formula (II):

wherein a, b, M, A and q are as defined hereinbefore and Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein Y has an average carbon content of from about 10.0 to about 14.0 (preferably from about 11.0 to about 13.0, more preferably 11.5 to 12.5 carbon atoms); (preferably said mixture of nonbranched alkylbenzenesulfonates is further characterized by a sum of carbon atoms in Y, of from 9 to 15, more preferably 10 to 14); and wherein said composition is further characterized by a 2/3-phenyl index of from about 350 to about 10,000 (preferably from about 400 to about 1200, more preferably from about 500 to about 700) (and also preferably wherein said surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3, preferably less than about 0.2, more preferably less than about 0.1, more preferably still, from 0 to 0.05).

Also encompassed by way of mid-chain branched surfactants of the alkylbenzene- derived types are surfactant mixtures comprising the product of a process comprising the steps of: alkylating benzene with an alkylating mixture; sulfonating the product of (I); and neutralizing the product of (LI); wherein said alkylating mixture comprises: (a) from about 1% to about 99.9%o, by weight of branched C₇-C₂₀ monoolefins, said branched monoolefϊns having structures identical with those of the branched monoolefins formed by dehydrogenating branched parafins of formula RΕR² wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls; R¹ is

to C₃ alkyl; and R² is selected from H and Ci to C₃ alkyl; and (b) from about 0.1 %> to about 85%, by weight of C7-C20 linear aliphatic olefins; wherein said alkylating mixture contains said branched C7-C20 monoolefins having at least two different carbon numbers in said C₇-C₂o range, and has a mean carbon content of from about 9.5 to about 14.5 carbon atoms; and wherein said components (a) and (b) are at a weight ratio of at least about 15:85.

Bleaching System - The laundry compositions of the present invention may comprise a bleaching system. Bleaching systems typically comprise a "bleaching agent" (source of hydrogen peroxide) and an "initiator" or "catalyst". When present, bleaching agents will typically be at levels of from about 1%, preferably from about 5% to about 30%, preferably to about 20% by weight of the composition. If present, the amount of bleach activator will typically be from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight, of the bleaching composition comprising the bleaching agent-plus-bleach activator.

Bleaching Agents - Hydrogen peroxide sources are described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)", and include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms.

The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Also useful are sources of available oxygen such as persulfate bleach (e.g., OXONE, manufactured by DuPont). Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources 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 smaller 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 a silicate, borate or water- soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleaching agent a chlorine-type bleaching material. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine-type bleaches are less preferred for compositions which comprise enzymes.

(a) Bleach Activators - Preferably, the peroxygen bleach component in the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%), preferably to about 10%, more preferably to about 8%, by weight of the composition. Preferred activators are selected from the group consisting of tetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3- chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C\Q- OBS), benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (Cg-OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonaoyl) amino hexanoyloxy] -benzene sulfonate sodium salt (NACA-OBS) an example of which is described in U.S. Patent No.

5,523,434, dodecanoyloxybenzenesulphonate (LOBS or C12-OBS), 10- undecenoyloxybenzenesulfonate (UDOBS or C J I-OBS with unsaturation in the 10 position), and decanoyloxybenzoic acid (DOB A). Preferred bleach activators are those described in U.S. 5,698,504 Christie et al., issued December 16, 1997; U.S. 5,695,679 Christie et al. issued December 9, 1997; U.S.

5,686,401 Willey et al., issued November 1 1, 1997; U.S. 5,686,014 Hartshorn et al., issued November 11, 1997; U.S. 5,405,412 Willey et al., issued April 11, 1995; U.S.

5,405,413 Willey et al., issued April 11, 1995; U.S. 5,130,045 Mitchel et al, issued July 14, 1992; and U.S. 4,412,934 Chung et al., issued November 1, 1983, and copending patent applications U. S. Serial Nos. 08/709,072, 08/064,564, all of which are incorporated herein by reference.

The mole ratio of peroxygen bleaching compound (as AvO) to bleach activator in the present invention generally ranges from at least 1 : 1, preferably from about 20: 1, more preferably from about 10:1 to about 1 :1, preferably to about 3:1.

Quaternary substituted bleach activators may also be included. The present laundry compositions preferably comprise a quaternary substituted bleach activator

(QSBA) or a quaternary substituted peracid (QSP); more preferably, the former. Preferred

QSBA structures are further described in U.S. 5,686,015 Willey et al., issued November 11, 1997; U.S. 5,654,421 Taylor et al., issued August 5, 1997; U.S. 5,460,747 Gosselink et al., issued October 24, 1995; U.S. 5,584,888 Miracle et al., issued December 17, 1996; and U.S. 5,578,136 Taylor et al., issued November 26, 1996; all of which are incorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substituted as described in U.S. 5,698,504, U.S. 5,695,679, and U.S. 5,686,014 each of which are cited herein above. Preferred examples of such bleach activators include: (6- octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl) oxybenzenesulfonate,

(6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof. Other useful activators, disclosed in U.S. 5,698,504, U.S. 5,695,679, U.S.

5,686,014 each of which is cited herein above and U.S. 4,966,723Hodge et al., issued

October 30, 1990, include benzoxazin-type activators, such as a C₆H ring to which is fused in the 1,2 -positions a moiety ~C(O)OC(R^)=N-.

Depending on the activator and precise application, good bleaching results can be obtained from bleaching systems having with in-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5. Typically, for example, activators with electron-withdrawing moieties are used for near-neutral or sub-neutral pH ranges.

Alkalis and buffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. 5,698,504, U.S. 5,695,679 and U.S. 5,686,014, each of which is cited herein above, are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639 Willey et al., issued April 2, 1996 incorporated herein by reference).

(b) Organic Peroxides, especially Diacyl Peroxides - These are extensively illustrated in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982 at pages 27-90 and especially at pages 63-72, all incorporated herein by reference. If a diacyl peroxide is used, it will preferably be one which exerts minimal adverse impact on spotting/filming.

(c) Metal-containing Bleach Catalysts - The present invention compositions and methods may utilize metal-containing bleach catalysts that are effective for use in bleaching compositions. Preferred are manganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. 4,430,243 Bragg, issued February 2, 1982.

Manganese Metal Complexes - If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent Nos. 5,576,282; 5,246,621; 5,244,594; 5,194,416; and 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al;

Preferred examples of these catalysts include Mn^2(^u~C)3( _>7-trimefhyl-l,4,7-

triazacyclononane)2(PF6)2_> MnHL^u-O) \ (u-OAc)2( 1 ,4,7-trimethyl- 1 ,4,7- triazacyclononane)2(ClO_ι)2, Mnl ^u-O^ 1 ,4,7-triazacyclononane)4(ClO_ι)4, Mn^^" Mn^rV4(u-O)ι(u-OAc)2.(l,4,7-trimethyl-l,4,7-triazacyclononane)2(Clθ4)3, Mn^IV(l,4,7- trimethyl-l,4,7-triazacyclononane)- (OCH3)3(PFg), and mixtures thereof. Other metal- based bleach catalysts include those disclosed in U.S. Patent Nos. 4,430,243 and U.S. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following: U.S. Patent Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,1 17; 5,274,147; 5,153,161; and 5,227,084.

Cobalt Metal Complexes - Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; and M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg.

Mech.. (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T_y, wherein "OAc" represents an acetate moiety and "T_v" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2; [Co(NH₃)₅OAc](PF₆)2; [Co(NH3)₅OAc](SO₄); [Co(NH₃)5OAc3(BF₄)2; and [Co(NH3)₅OAc](NO )2 (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936; 5,595,967; and 5,703,030; in the Tobe article and the references cited therein; and in U.S. Patent 4,810,410; J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inorg. Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry. 56, 22-25 (1952). Transition Metal Complexes of Macropolycyclic Rigid Ligands -Compositions herein may also suitably include as bleach catalyst a transition metal complex of a macropolycyclic rigid ligand. The phrase "macropolycyclic rigid ligand" is sometimes abbreviated as "MRL" in discussion below. The amount used is a catalytically effective amount, suitably about 1 ppb or more, for example up to about 99.9%, more typically about 0.001 ppm or more, preferably from about 0.05 ppm to about 500 ppm (wherein "ppb" denotes parts per billion by weight and "ppm" denotes parts per million by weight). Suitable transition metals e.g., Mn are illustrated hereinafter. "Macropolycyclic" means a MRL is both a macrocycle and is polycyclic. "Polycyclic" means at least bicyclic. The term "rigid" as used herein herein includes "having a superstructure" and "cross- bridged". "Rigid" has been defined as the constrained converse of flexibility: see D.H. Busch., Chemical Reviews., (1993), 93, 847-860, incorporated by reference. More particularly, "rigid" as used herein means that the MRL must be determinably more rigid than a macrocycle ("parent macrocycle") which is otherwise identical (having the same ring size and type and number of atoms in the main ring) but lacking a superstructure (especially linking moieties or, preferably cross-bridging moieties) found in the MRL's. In determining the comparative rigidity of macrocycles with and without superstructures, the practitioner will use the free form (not the metal-bound form) of the macrocycles. Rigidity is well-known to be useful in comparing macrocycles; suitable tools for determining, measuring or comparing rigidity include computational methods (see, for example, Zimmer, Chemical Reviews. (1995), 95(38), 2629-2648 or Hancock et al., Inorganica Chimica Acta. (1989), 164, 73-84.

Preferred MRL's herein are a special type of ultra-rigid ligand which is cross- bridged. A "cross-bridge" is nonlimitingly illustrated in 1.11 hereinbelow. In 1.11, the cross-bridge is a -CH2CH2- moiety. It bridges N 1 and N 8 in the illustrative structure. By

comparison, a "same-side" bridge, for example if one were to be introduced across N and N 12 in 1.11, would not be sufficient to constitute a "cross-bridge" and accordingly would not be preferred.

Suitable metals in the rigid ligand complexes include Mn(II), Mn(m), Mn(IV),

Mn(V), Fe(LT), Fe(III), Fe(IV), Co(I), Co(II), Co(LTI), Ni(Q, Ni(II), Ni(m), Cu(I), Cu(LT),

Cu(iπ), Cr(IJ), Cr(Ln), Cr(rV), Cr(V), Cr(VI), V(m), V(ΓV), V(V), MO(ΓV), MO(V), Mo(VI), W(rV), W(V), W(VI), Pd(LT), Ru(LI), Ru(IJI), and Ru(IV). Preferred transition- metals in the instant transition-metal bleach catalyst include manganese, iron and chromium.

More generally, the MRL's (and the corresponding transition-metal catalysts) herein suitably comprise: (a) at least one macrocycle main ring comprising four or more heteroatoms; and

(b) a covalently connected non-metal superstructure capable of increasing the rigidity of the macrocycle, preferably selected from (i) a bridging superstructure, such as a linking moiety; (ii) a cross-bridging superstructure, such as a cross-bridging linking moiety; and (iii) combinations thereof. The term "superstructure" is used herein as defined in the literature by Busch et al., see, for example, articles by Busch in "Chemical Reviews".

Preferred superstructures herein not only enhance the rigidity of the parent macrocycle, but also favor folding of the macrocycle so that it co-ordinates to a metal in a cleft. Suitable superstructures can be remarkably simple, for example a linking moiety such as any of those illustrated in Fig. 1 and Fig. 2 below, can be used.

Fig. 1 wherein n is an integer, for example from 2 to 8, preferably less than 6, typically 2 to 4, or

Fig. 2 wherein m and n are integers from about 1 to 8, more preferably from 1 to 3; Z is N or CH; and T is a compatible substituent, for example H, alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. The aromatic ring in 1.10 can be replaced by a saturated ring, in which the atom in Z connecting into the ring can contain N, O, S or C.

Suitable MRL's are further nonlimitingly illustrated by the following compound:

Fig. 3

This is a MRL in accordance with the invention which is a highly preferred, cross- bridged, methyl-substituted (all nitrogen atoms tertiary) derivative of cyclam. Formally, this ligand is named 5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane using the extended von Baeyer system. See "A Guide to IUPAC Nomenclature of Organic Compounds: Recommendations 1993", R. Panico, W.H. Powell and J-C Richer (Eds.), Blackwell Scientific Publications, Boston, 1993; see especially section R-2.4.2.1.

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which are suitable for use in the invention compositions can in general include known compounds where they conform with the definition herein, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry or laundry uses, and non-limitingly illustrated by any of the following:

Dichloro-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(LI) Diaquo-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate Aquo-hydroxy-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(lH)

Hexafluorophosphate Diaquo-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

Dichloro-5,12-dimethyl-l,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(rLT)

Hexafluorophosphate Dichloro-5,12-di-n-butyl-l,5,8,12-tetraaza bicyclo[6.6.2]hexadecaneManganese(IT) Dichloro-5, 12-dibenzyl- 1 ,5,8, 12-tetraazabicyclo[6.6.2]hexadecaneManganese(π) Dichloro-5-n-butyl-12-methyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(LI) Dichloro-5-n-octyl-12-methyl-l,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane

Manganese(LI) Dichloro-5 -n-butyl- 12-methyl- 1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(H).

As a practical matter, and not by way of limitation, the compositions and laundry processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic washing process, typical compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the bleaching compositions. (d) Other Bleach Catalysts - The compositions herein may comprise one or more other bleach catalysts. Preferred bleach catalysts are zwitterionic bleach catalysts, which are described in U.S. Patent No. 5,576,282 (especially 3-(3,4-dihydroisoquinolinium) propane sulfonate. Other bleach catalysts include cationic bleach catalysts are described in U.S. Patent Nos. 5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO 95/13351, WO 95/13352, and WO 95/13353.

Also suitable as bleaching agents are preformed peracids, such as phthalimido- peroxy-caproic acid ("PAP"). See for example U.S. Patent Nos. 5,487,818, 5,310,934, 5,246,620, 5,279,757 and 5,132,431.

Enzymes - With respect to the enzymes in the particulate solid of the present invention, any suitable enzyme can be used. The preferred enzymes for use in the particulate solids of the present invention are selected from proteases, amylases, cellulases and mixtures thereof. Nonlimiting examples of other suitable enzymes include the following:

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, mannanases, more preferably plant cell wall degrading enzymes and non-cell wall-degrading enzymes (WO 98/39403 A) and can, more specifically, include pectinase (WO 98/06808 A, JP10088472 A, JP10088485 A); pectolyase (WO98/06805 Al); pectin lyases free from other pectic enzymes (WO9806807 Al); chondriotinase ( EP 747,469 A); xylanase ( EP 709,452 A, WO 98/39404 A, WO98/39402 A) including those derived from microtetraspora βexuosa (US 5683911); isopeptidase (WO 98/16604 A); keratinase (EP 747,470 A, WO 98/40473 A); lipase ( GB 2,297,979 A; WO 96/16153 A; WO 96/12004 A; EP 698,659 A; WO 96/16154 A); cellulase or endoglucanase (GB 2,294,269 A; WO 96/27649 A; GB 2,303,147 A; WO98/03640 A; see also neutral or alkaline cellulases derived from chrysosporium lucknowense strain VKM F-3500D as disclosed in WO9815633 A); polygalacturonase (WO 98/06809 A); mycodextranase (WO 98/13457 A); thermitase (WO 96/28558 A) cholesterol esterase (WO 98 28394 A); or any combination thereof; and known amylases oxidoreductases; oxidases or combination systems including same (DE19523389 Al ) mutant blue copper oxidases (WO9709431 Al), peroxidases (see for example US 5,605,832, WO97/31090 Al), mannanases (WO9711164 Al); laccases, see WO9838287 Al or WO9838286 Al or for example, those laccase variants having amino acid changes in myceliophthora or scytalidium laccase(s) as described in WO9827197 Al or mediated laccase systems as described in DEI 9612193 Al), or those derived from coprinus strains (see, for example WO9810060 Al or WO9827198 Al), phenol oxidase or polyphenol oxidase (JP10174583 A) or mediated phenol oxidase systems (WO9711217 A); enhanced phenol oxidase systems (WO 9725468 A WO9725469 A); phenol oxidases fused to an amino acid sequence having a cellulose binding domain (WO9740127 Al, WO9740229 Al) or other phenol oxidases (WO9708325 A, WO9728257 Al) or superoxide dismutases. Oxidoreductases and/or their associated antibodies can be used, for example with H₂O₂, as taught in WO 98/07816 A. Depending on the type of detergent composition, other redox-active enzymes can be used, even, for example, catalases (see, for example JP09316490 A). Also useful herein are any oxygenases of extracellular origin, especially fungal oxygenase such as dioxygenase of extracellular origin. The latter is most especially quercetinase, catechinase or an anthocyanase, optionally in combination with other suitable oxidase, peroxidase or hydrolytic enzymes, all a taught in WO9828400 A2.

Examples of such suitable enzymes and/or levels of use are disclosed in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950

The cellulases useful in the present invention include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, J61078384 and WO96/02653 which discloses fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 73^'9 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS- 2.247.832 and WO95/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. fhermoidea), particularly the Humicola strain DSM 1800. Other suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a ~43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in WO 91/17243. Also suitable cellulases are the EGffl cellulases from Trichoderma longibrachiatum described in WO94/21801 to Genencor. Especially suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A S) are especially useful. See also WO91/17244 and WO91/21801. Other suitable cellulases for fabric care and or laundry properties are described in WO96/34092, WO96/17994 and WO95/24471.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach enhancing molecule. 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. Suitable peroxidases and peroxidase-containing detergent compositions are disclosed, for example, in U.S. Patent Nos. 5,705,464, 5,710,115, 5,576,282, 5,728,671 and 5,707,950, PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

Suitable enhancers are selected from the group consisting of substituted phenthiazine and phenoxasine 10-Phenothiazinepropionicacid (PPT), 10- ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621), substituted syringates (C3-C5 substituted alkyl syringates), phenols and mixtures thereof. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Enzymatic systems may be used as bleaching agents. The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application

91202655.6 filed October 9, 1991.

Other preferred enzymes that can be included in the laundry compositions of the present invention include lipases. 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. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as Ml Lipase^- ^an<1 Lipomax^- (Gist-Brocades) and Lipolase^- and Lipolase

UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention. Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever. Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to laundry compositions have been described in e.g. WO-A-88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). In addition to the above referenced lipases, phospholipases may be incorporated into the laundry compositions of the present invention. Nonlimiting examples of suitable phospholipases included: EC 3.1.1.32 Phospholipase Al ; EC 3.1.1.4 Phospholipase A2; EC 3.1.1.5 Lysopholipase; EC 3.1.4.3 Phospholipase C; EC 3.1.4.4. Phospolipase D.

Commercially available phospholipases include LECITASE® from Novo Nordisk A/S of Denmark and Phospholipase A2 from Sigma. When phospolipases are included in the compositions of the present invention, it is preferred that amylases are also included. Without desiring to be bound by theory, it is believed that the combined action of the phospholipase and amylase provide substantive stain removal, especially on greasy/oily, starchy and highly colored stains and soils. Preferably, the phospholipase and amylase, when present, are incorporated into the compositions of the present invention at a pure enzyme weight ratio between 4500: 1 and 1 :5, more preferably between 50: 1 and 1 :1.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Suitable is the protease called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which Lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.

A preferred protease referred to as "Protease D" is a carbonyl hydrolase as described in U.S. Patent No. 5,677,272, and WO95/10591. Also suitable is a carbonyl hydrolase variant of the protease described in WO95/ 10591, having an amino acid sequence derived by replacement of a plurality of amino acid residues replaced in the precursor enzyme corresponding to position +210 in combination with one or more of the following residues : +33, +62, +67, -r76, +100, +101, +103, +104, +107, +128, +129, + 130, +132, +135, +156, +158, +164, -166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position corresponds to naturally-occurring subtilisin from Bacillus amylohquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins, such as Bacillus lentus subtilisin (co-pending patent application US Serial No. 60/048,550, filed June 04, 1997 and PCT International Application Serial No. PCT/LB98/00853).

Also suitable for the present invention are proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCLMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

Particularly useful proteases are described in PCT publications: WO 95/30010; WO 95/30011; and WO 95/29979. Suitable proteases are commercially available as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and

KANNASE® all from Novo Nordisk A S of Denmark, and as MAXATASE®,

MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of The Netherlands).

Preferred proteases useful herein include certain variants ( WO 96/28566 A; WO 96/28557 A; WO 96/28556 A; WO 96/25489 A).

Other particularly useful proteases are multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at an amino acid residue position corresponding to position 103 of Bacillus amylohquefaciens subtilisin in combination with a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61 , 62, 68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amylohquefaciens subtilisin; wherein when said protease variant includes a substitution of amino acid residues at positions corresponding to positions 103 and 76, there is also a substitution of an amino acid residue at one or more amino acid residue positions other than amino acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillus amylohquefaciens subtilisin and/or multiply-substituted protease variants comprising a substitution of an amino acid residue with another naturally occurring amino acid residue at one or more amino acid residue positions corresponding to positions 62, 212, 230, 232, 252 and 257 of Bacillus amylohquefaciens subtilisin as described in PCT Publication Nos. WO 99/20727, WO 99/20726, WO 99/20770 and WO 99/20769 to The Procter & Gamble Company and Genencor International, Inc., and PCT Publication No. WO 99/20723 to The Procter & Gamble Company. More preferably the protease variant includes a substitution set selected from the group consisting of:

12/76/ 103/ 104/ 130/222/245/261 ; 62/103/104/159/232/236/245/248/252; 62/103/104/159/213/232/236/245/248/252;

62/101/103/104/159/212/213/232/236/245/248/252;

68/103/104/159/232/236/245;

68/103/104/159/230/232/236/245;

68/103/104/159/209/232/236/245; 68/103/104/159/232/236/245/257;

68/76/103/104/159/213/232/236/245/260; 68/103/104/159/213/232/236/245/248/252;

68/103/104/159/183/232/236/245/248/252;

68/103/104/159/185/232/236/245/248/252;

68/103/104/159/185/210/232/236/245/248/252; 68/103/104/159/210/232/236/245/248/252;

68/103/104/159/213/232/236/245;

98/103/104/159/232/236/245/248/252;

98/102/103/104/159/212/232/236/245/248/252;

101/103/104/159/232/236/245/248/252; 102/103/104/159/232/236/245/248/252;

103/104/159/230/236/245;

103/104/159/232/236/245/248/252;

103/104/159/217/232/236/245/248/252;

103/104/130/159/232/236/245/248/252; 103/104/131/159/232/236/245/248/252;

103/104/159/213/232/236/245/248/252; and 103/104/159/232/236/245.

Still even more preferably the protease variant includes a substitution set selected from the group consisting of:

12R/76D/103A 104T/130T/222S/245R 261D; 62D/103A 104I/159D/232V/236H/245R 248D/252K; 62D/103 All 041/159D/213R/232V/236H/245R/248D/252K; 68A/103 All 041/159D/209W/232V/236H/245R;

68A 76D/103A/104I/159D/213R/232V/236H/245R/260A;

68A 103A 104I/159D/213E/232V/236H/245R/248D/252K;

68A/103A/104I/159D/183D/232V/236H/245R/248D/252K;

68 A/103 All 041/159D/232V/236H/245R; 68A/103A/104I/159D/230V/232V/236H/245R;

68A/103 All 041/159D/232V/236H/245R/257V; 68A 103 A/1041/159D/213G/232V/236H/245R/248D/252K;

68A/103A 104I/159D/185D/232V/236H/245R/248D/252K;

68A/103 A/1041/159D/185D/210L/232V/236H/245R/248D/252K;

68 A/103 A 1041/159D/210L/232V/236H/245R/248D/252K; 68A/103 A/1041/159D/213G/232V/236H/245R;

98L/103 A/1041/159D/232V/236H/245R/248D/252K;

98L/102A/103A/104I/159D/212G/232V/236H/245R 248D/252K;

101G/103A 104I/159D/232V/236H/245R/248D/252K;

102A/103A 104I/159D/232V/236H/245R/248D/252K; 103A/104I/159D/230V/236H/245R;

103A/104I/159D/232V/236H/245R/248D/252K;

103A/104I/159D/217E/232V/236H/245R/248D/252K;

103 A/1041/130G/159D/232V/236H/245R/248D/252K;

103A/104I/131V/159D/232V/236H/245R 248D/252K; 103 A 1041/159D/213R/232V/236H/245R 248D/252K; and

103 All 041/159D/232 V/236H/245R.

Most preferably the protease variant includes the substitution set 101/103/104/159/232/236/245/248/252, preferably 101G/103A 104I/159D/232V/ 236H/245R/248D/252K.

Bleach/amylase/protease combinations (EP 755,999 A; EP 756,001 A; EP 756,000 A) are also useful.

Also in relation to enzymes herein, enzymes and their directly linked inhibitors, e.g., protease and its inhibitor linked by a peptide chain as described in WO 98/13483 A, are useful in conjunction with the present hybrid builders. Enzymes and their non-linked inhibitors used in selected combinations herein include protease with protease inhibitors selected from proteins, peptides and peptide derivatives as described in WO 98/13461 A, WO 98/13460 A, WO 98/13458 A, WO 98/13387 A.

Amylases can be used with amylase antibodies as taught in WO 98/07818 A and WO 98/07822 A, lipases can be used in conjunction with lipase antibodies as taught in

WO 98/07817 A and WO 98/06810 A, proteases can be used in conjunction with protease antibodies as taught in WO 98/07819 A and WO 98/06811 A, Cellulase can be combined with cellulase antibodies as taught in WO 98/07823 A and WO 98/07821 A. More generally, enzymes can be combined with similar or dissimilar enzyme directed antibodies, for example as taught in WO 98/07820 A or WO 98/06812 A. The preferred enzymes herein can be 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, fhermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Amylases (α and/or β) can be included for removal of carbohydrate-based stains. WO94/02597 describes laundry compositions which incorporate mutant amylases. See also WO95/ 10603. Other amylases known for use in laundry compositions include both α- and β-amylases. α-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amylases described in WO94/18314 and WO96/05295, Genencor, and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603. Also suitable are amylases described in EP 277 216.

Examples of commercial α-amylases products are Purafect Ox Am® from

Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A S Denmark. WO95/26397 describes other suitable amylases : α-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to

10, measured by the Phadebas® α-amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382. The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Nowadays, it is common practice to modify wild-type enzymes via protein / genetic engineering techniques in order to optimize their performance efficiency in the laundry detergent and/or fabric care compositions of the invention. For example, the variants may be designed such that the compatibility of the enzyme to commonly encountered ingredients of such compositions is increased. Alternatively, the variant may be designed such that the optimal pH, bleach or chelant stability, catalytic activity and the like, of the enzyme variant is tailored to suit the particular laundry application.

In particular, attention should be focused on amino acids sensitive to oxidation in the case of bleach stability and on surface charges for the surfactant compatibility. The isoelectric point of such enzymes may be modified by the substitution of some charged amino acids, e.g. an increase in isoelectric point may help to improve compatibility with anionic surfactants. The stability of the enzymes may be further enhanced by the creation of e.g. additional salt bridges and enforcing calcium binding sites to increase chelant stability.

Other suitable cleaning adjunct materials that can be added are enzyme oxidation scavengers. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.

A range of enzyme materials are also disclosed in WO 9307263 and WO 9307260 to Genencor International, WO 8908694, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, and in U.S. 4,507,219. Enzyme materials particularly useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868. Enzyme Stabilizers - Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, EP 199,405 and EP 200,586. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532. The enzymes employed herein can be 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. Suitable enzyme stabilizers and levels of use are described in U.S. Pat. Nos. 5,705,464, 5,710,115 and 5,576,282.

Builders - The detergent and laundry compositions described herein preferably comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1% builder, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to about 30%) by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Preferred builders for use in the detergent and laundry compositions, particularly dishwashing compositions, described herein include, but are not limited to, water-soluble builder compounds, (for example polycarboxylates) as described in U.S. Patent Nos. 5,695,679, 5,705,464 and 5,710,115. Other suitable polycarboxylates are disclosed in U.S. Patent Nos. 4,144,226, 3,308,067 and 3,723,322. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly titrates.

Inorganic or P-containing 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 (see, for example, U.S. Patent Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, 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.

Suitable silicates include the water-soluble sodium silicates with an SiO₂:Na₂O ratio of from about 1.0 to 2.8, with ratios of from about 1.6 to 2.4 being preferred, and about 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO :Na₂O ratio of 2.0 is the most preferred. Silicates, when present, are preferably present in the detergent and laundry compositions described herein at a level of from about 5% to about 50% by weight of the composition, more preferably from about 10% to about 40% by weight.

Partially soluble or insoluble builder compounds, which are suitable for use in the detergent and laundry compositions, particularly granular detergent compositions, include, but are not limited to, crystalline layered silicates, preferably crystalline layered sodium silicates (partially water-soluble) as described in U.S. Patent No. 4,664,839, and sodium aluminosilicates (water-insoluble). When present in detergent and laundry compositions, these builders are typically present at a level of from about 1% to 80%_> by weight, preferably from about 10%> to 70% by weight, most preferably from about 20%_> to 60%) by weight of the composition.

Crystalline layered sodium silicates having the general formula NaMSi_xθ2χ+i -yH2θ wherein M is sodium or hydrogen, x is a number from about 1.9 to about 4, preferably from about 2 to about 4, most preferably 2, and y is a number from about 0 to about 20, preferably 0 can be used in the compositions described herein. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. The most preferred material is delta-Na2SiO5, available from Hoechst AG as NaSKS-6

(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. SKS-6 is a highly preferred layered silicate for use in the compositions described herein herein, but other such layered silicates, such as those having the general formula NaMSi_xθ2χ+l-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 in the compositions described 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-Na2Siθ5 (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. The crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionizable material. The solid, water-soluble ionizable material is preferably selected from organic acids, organic and inorganic acid salts and mixtures thereof. 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 have the empirical formula:

[M_z(AlO₂)_y]-xH₂O 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. Preferably, the aluminosilicate builder is an aluminosilicate zeolite having the unit cell formula:

Na_z[(AlO₂)_z(SiO₂)_y] xH₂O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably from 10 to 264. The aluminosilicate builders are preferably in hydrated form and are preferably crystalline, containing from about 10%> to about 28%, more preferably from about 18% to about 22%> water in bound form.

These aluminosilicate ion exchange materials 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. 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP and Zeolite HS and mixtures thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2[(AlO₂)i2(SiO2)i2]- H₂O 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. Zeolite X has the formula: Na₈₆[(AlO2)86(SiO₂)i06]-276H₂O 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 zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions described herein are the 3,3-dicar- boxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984. Useful succinic acid builders include the C5-C20 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. Fatty acids, e.g., C12-C1 g 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. Dispersants - One or more suitable polyalkyleneimine dispersants may be incorporated into the laundry compositions of the present invention. Examples of such suitable dispersants can be found in European Patent Application Nos. 111,965, 111,984, and 112,592; U.S. Patent Nos. 4,597,898, 4,548,744, and 5,565,145. However, any suitable clay/soil dispersent or anti-redepostion agent can be used in the laundry compositions of the present invention.

In addition, polymeric dispersing agents which include polymeric polycarboxylates and polyethylene glycols, are suitable for use in the present invention. 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. 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 U.S. 3,308,067.

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, 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/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

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. Soil Release Agents - The compositions according to the present invention may optionally comprise one or more soil release agents. If utilized, soil release agents will generally comprise from about 0.01%, preferably from about 0.1%, more preferably from about 0.2% to about 10%, preferably to about 5%, more preferably to about 3% by weight, of the composition. Nonlimiting examples of suitable soil release polymers are disclosed in: U.S. Patent Nos. 5,728,671; 5,691,298; 5,599,782; 5,415,807; 5,182,043; 4,956,447; 4,976,879; 4,968,451; 4,925,577; 4,861,512; 4,877,896; 4,771,730; 4,711,730; 4,721,580; 4,000,093; 3,959,230; and 3,893,929; and European Patent Application 0 219 048. Further suitable soil release agents are described in U.S. Patent Nos. 4,201,824;

4,240,918; 4,525,524; 4,579,681; 4,220,918; and 4,787,989; EP 279,134 A; EP 457,205 A; and DE 2,335,044.

Chelating Agents - The compositions of the present invention herein may also optionally contain a chelating agent which serves to chelate metal ions and metal impurities which would otherwise tend to deactivate the bleaching agent(s). Useful chelating agents can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Further examples of suitable chelating agents and levels of use are described in U.S. Pat. Nos. 5,705,464, 5,710,115, 5,728,671 and 5,576,282. The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents will generally comprise from about 0.1 % to about 15%), more preferably from about 0.1% to about 3.0%> by weight of the detergent compositions herein.

Suds suppressor - Another optional ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures. Examples of suitable suds suppressers are disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. These suds suppressers are normally employed at levels of from 0.001% to 2%> by weight of the composition, preferably from 0.01 % to 1 % by weight. Softening agents - Fabric softening agents can also be incorporated into laundry detergent compositions in accordance with the present invention. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in U.S. 5,019,292. Organic softening agents include the water insoluble tertiary amines as disclosed in GB-A-1 514 276 and EP-B-011 340 and their combination with mono C12- C14 quaternary ammonium salts are disclosed in EP-B-026 527 and EP-B-026 528 and di-long-chain amides as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146. Particularly suitable fabric softening agents are disclosed in U.S. Patent Nos.

5,707,950 and 5,728,673.

Levels of smectite clay are normally in the range from 2% to 20%>, more preferably from 5% to 15% by weight, with the material being added as a dry mixed component to the remainder of the formulation. Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5%> to 5% by weight, normally from 1%> to 3%> by weight whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 %> to 2%, normally from 0.15% to 1.5% by weight. These materials are normally added to the spray dried portion of the composition, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as molten liquid on to other solid components of the composition.

Biodegradable quaternary ammonium compounds as described in EP-A-040 562 and EP-A-239 910 have been presented as alternatives to the traditionally used di-long alkyl chain ammonium chlorides and methyl sulfates. Non-limiting examples of softener-compatible anions for the quaternary ammonium compounds and amine precursors include chloride or methyl sulfate.

Dye transfer inhibition - The detergent compositions of the present invention can also include compounds for inhibiting dye transfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering and conditioning operations involving colored fabrics. . Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention can also comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.

Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Examples of such dye transfer inhibiting agents are disclosed in U.S. Patent Nos. 5,707,950 and 5,707,951.

Additional suitable dye transfer inhibiting agents include, but are not limited to, cross-linked polymers. Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly with active groups n the backbone or on branches; cross-linked polymers have been described in the Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way that they form a three-dimensional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymers entrap the dyes by swelling. Such cross-linked polymers are described in the co-pending European patent application 94870213.9.

Addition of such polymers also enhances the performance of the enzymes according the invention. pH and Buffering Variation - Many of the detergent and laundry compositions described herein will be buffered, i.e., they are relatively resistant to pH drop in the presence of acidic soils. However, other compositions herein may have exceptionally low buffering capacity, or may be substantially unbuffered. Techniques for controlling or varying pH at recommended usage levels more generally include the use of not only buffers, but also additional alkalis, acids, pH-jump systems, dual compartment containers, etc., and are well known to those skilled in the art. Other Materials - Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more materials for assisting or enhancing laundry performance, treatment of the substrate to be cleaned, or designed to improve the aesthetics of the compositions. Adjuncts which can also be included in compositions of the present invention, at their conventional art-established levels for use (generally, adjunct materials comprise, in total, from about 30% to about 99.9%, preferably from about 70%) to about 95%), by weight of the compositions), include other active ingredients such as non-phosphate builders, color speckles, silvercare, anti-tarnish and/or anti- cooosion agents, dyes, fillers, germicides, alkalinity sources, hydrotropes, anti-oxidants, perfumes, solubilizing agents, carriers, processing aids, pigments, and pH control agents as described in U.S. Patent Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014 and 5,646,101.

Methods of Laundry - In addition to the methods for laundry fabrics described herein, the invention herein also encompasses a laundering pretreatment process for fabrics which have been soiled or stained comprising directly contacting said stains and/or soils with a highly concentrated form of the laundry composition set forth above prior to washing such fabrics using conventional aqueous washing solutions. Preferably, the laundry composition remains in contact with the soil/stain for a period of from about 30 seconds to 24 hours prior to washing the pretreated soiled/stained substrate in conventional manner. More preferably, pretreatment times will range from about 1 to 180 minutes. PRODUCT WITH INSTRUCTIONS FOR USE

The present invention also encompasses the inclusion of instructions on the use of the particulate solid containing compositions of the present invention with the packages containing the compositions herein or with other forms of advertising associated with the sale or use of the compositions. The instructions may be included in any manner typically used by consumer product manufacturing or supply companies. Examples include providing instructions on a label attached to the container holding the composition; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other written or oral instructions which may be connected to the purchase or use of the compositions. Specifically the instructions will include a description of the use of the composition, for instance, the recommended amount of composition to use in a washing machine to clean the fabric; the recommended amount of composition to apply to the fabric; if soaking or rubbing is appropriate . The compositions of the present invention are preferably included in a product.

The product preferably comprises a composition comprising one or more low density filler particles of the present invention and one or more particulate solids of the present invention, and optionally one or more cleaning adjunct materials, and further comprises instructions for using the product to launder fabrics by contacting a fabric in need of cleaning with an effective amount of the composition such that the composition cleans the fabric.

The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention. In all of the following examples Protease¹ means a protease variant comprising substitution of amino acid residues with another naturally occurring amino acid residue at positions corresponding to positions

101G/103All04V159O/232VI236W245R1248OI252K oϊ Bacillus amylohquefaciens subtilisin. Protease¹ can be substituted with any other additional protease variant of the present invention, with substantially similar results in the following examples.

In the cleaning composition examples of the present invention, the Protease¹ enzyme levels are expressed by pure enzyme by weight of the total composition, the other enzyme levels are expressed by raw material by weight of the total composition, and unless otherwise specified, the other ingredients are expressed by weight of the total composition.

Further, in the following examples some abbreviations known to those of ordinary skill in the art are used, consistent with the disclosure set forth herein. Fabric cleaning compositions

Granular Fabric Cleaning Composition The granular fabric cleaning compositions of the present invention contain an effective amount of one or more protease enzymes, preferably from about 0.001%) to about 10%, more preferably, from about 0.005% to about 5%, more preferably from 0 01% to about 1% by weight of active protease enzyme of the composition. (See U.S. Patent No. 5,679,630 Examples).

Example 27

Granular Fabric Cleaning Composition

Example No.

Component A B C D

Protease¹ 0.10 0.20 0.03 0.05

Protease² - - 0.2 0.15

C 13 linear alkyl benzene sulfonate 22.00 22.00 22.00 22.00

Phosphate (as sodium 23.00 23.00 23.00 23.00 tπpolyphosphates)

Sodium carbonate 23.00 23.00 23.00 23.00

Sodium silicate 14.00 14.00 14.00 14.00

Zeolite 8.20 8.20 8.20 8.20

Chelant (diethylaenetnamine- 0.40 0.40 0.40 0.40 pentaacetic acid)

Sodium sulfate 5.50 5.50 5.50 5.50

Water balance to 100%

² Protease other than the Protease¹ including but not limited to the additional proteases useful in the present invention descπbed herein.

In Examples 27 C and D, any combination of the protease enzymes useful m the present invention recited herein, among others, are substituted for Protease¹ and Protease², with substantially similar results.

Example 2 Granular Fabnc Cleaning Composition

Example No.

Component A B C D

Protease¹ 0.10 0.20 0.03 0.05

Protease² - - 0.2 0.1

Cj2 alkyl benzene sulfonate 12.00 12.00 12.00 12.00

Zeolite A (1-10 micrometer) 26.00 26.00 26.00 26.00 C_j2-Ci4 secondary (2,3) alkyl sulfate, 5.00 5.00 5.00 5.00

Na salt

Sodium citrate 5.00 5.00 5.00 5.00

Optical bπghtener 0.10 0.10 0.10 0.10

Sodium sulfate 17.00 17.00 17.00 17.00

Fillers, water, minors balance to 100%

² Protease other than the Protease¹ including but not limited to the additional proteases useful in the present invention described herein.

In Examples 28 C and D, any combination of the protease enzymes useful in the present invention recited herein, among others, are substituted for Protease¹ and Protease², with substantially similar results.

Example 29 Granular Fabnc Cleaning Compositions Components Example No.

A B

Linear alkyl benzene sulphonate 11.4 10.70 Tallow alkyl sulfate 1.80 2.40 Ci4_ι 5 alkyl sulfate 3.00 3.10

^14-15 alcohol 7 times ethoxylated 4.00 4.00

Tallow alcohol 11 times ethoxylated 1.80 1.80

Dispersant 0.07 0.1

Sihcone fluid 0.80 0.80

Trisodium citrate 14.00 15.00

Citric acid 3.00 2.50

Zeolite 32.50 32.10

Maleic acid acrylic acid copolymer 5.00 5.00

Diethylene triamine penta methylene 1.00 0.20 phosphonic acid

Protease¹ 0.1 0.01 Lipase 0.36 0.40

Amylase 0.30 0.30

Sodium silicate 2.00 2.50

Sodium sulfate 3.50 5.20

Polyvinyl pyrrohdone 0.30 0.50

Perborate 0.5 1

Phenol sulphonate 0.1 0.2

Peroxidase 0.1 0.1

Minors Up to 100 Up to 100

Example 30

Granular Fabπc Cleaning Compositions

Examp^' le No.

Components A B

Sodium linear C \ 2 alkyl benzene-sulfonate 6.5 8.0

Sodium sulfate 15.0 18.0

Zeolite A 26.0 22.0

Sodium nitπlotriacetate 5.0 5.0

Polyvinyl pyrrolidone 0.5 0.7

Tetraacetylethylene diamine 3.0 3.0

Boric acid 4.0 -

Perborate 0.5 1

Phenol sulphonate 0.1 0.2

Protease¹ 0.02 0.05

Fillers (e.g., silicates; carbonates; perfumes; water) Up to 100 Up to 100

Example 31

Compact Granular Fabric Cleaning Composition

Components Weight %

Alkyl Sulfate 8.0

Alkyl Ethoxy Sulfate 2.0

Mixture of C25 and C45 alcohol 3 and 7 times ethoxylated 6.0

Polyhydroxy fatty acid amide 2.5 Zeolite 17 0

Layered silicate/citrate 16 0

Carbonate 7 0

Maleic acid acrylic acid copolymer 5 0

Soil release polymer 0 4

Carboxymethyl cellulose 0 4

Poly (4-vιnylpyπdιne) -N-oxide 0 1

Copolymer of vinylimidazole and vmylpyrrolidone 0 1

PEG2000 0 2

Protease¹ 0 03

Lipase 0 2

Cellulase 0 2

Tetracetylethylene diamme 6 0

Percarbonate 22 0

Ethylene diamme disuccmic acid 0 3

Suds suppressor 3 5

Dιsodιum-4,4'-bιs (2-morpholιno -4-anιlmo-s-tπazιn-6- 0 25 ylammo) stιlbene-2,2'-dιsulphonate

Dιsodιum-4,4'-bιs (2-sulfostyπl) biphenyl 0 05

Water, Perfume and Minors Up to 100

Example 32

Granular Fabric Cleaning Composition

Component Weight %

Linear alkyl benzene sulphonate 7.6

Cj g-Ci g alkyl sulfate 1.3

C 14.15 alcohol 7 times ethoxylated 4.0

Coco-alkyl-dimethyl hydroxyethyl ammonium chloride 1.4

Dispersant 0.07

Sihcone fluid 0.8

Tπsodium citrate 5.0

Zeolite 4A 15.0

Maleic acid acrylic acid copolymer 4.0

Diethylene triamine penta methylene phosphonic acid 0.4

Perborate 15.0

Tetraacetylethylene diamine 5.0

Smectite clay 10.0

Poly (oxy ethylene) (MW 300,000) 0.3

Protease¹ 0.02

Lipase 0.2

Amylase 0.3

Cellulase 0.2

Sodium silicate 3.0

Sodium carbonate 10.0

Carboxymethyl cellulose 0.2

Brighteners 0.2

Water, perfume and minors Up to 100

Example 33

Granular Fabric Cleaning Composition

Component Weight %

Linear alkyl benzene sulfonate 6.92

Tallow alkyl sulfate 2.05

Cl4^_15 alcohol 7 times ethoxylated 4.4

C 12-15 alkyl ethoxy sulfate - 3 times ethoxylated 0.16

Zeolite 20.2

Citrate 5.5

Carbonate 15.4

Silicate 3.0

Maleic acid acrylic acid copolymer 4.0

Carboxymethyl cellulase 0.31

Soil release polymer 0.30

Protease¹ 0.1

Lipase 0.36

Cellulase 0.13

Perborate tetrahydrate 11.64 Perborate monohydrate 8 7

Tetraacetylethylene diamine 5 0

Diethylene tramine penta methyl phosphonic acid 0 38

Magnesium sulfate 0.40

Bπghtener 0 19

Perfume, silicone, suds suppressors 0 85

Minors Up to 100

Example 34 Granular Fabric Cleaning Composition

Component A B C

Base Granule Components

LAS/AS/ AES (65/35) 9.95

LAS/AS/AES (70/30) - 12.05 7.70

Alummo silicate 14.06 15.74 17.10

Sodium carbonate 11.86 12.74 13.07

Sodium silicate 0.58 0.58 0.58

NaPAA Sohds 2.26 2.26 1.47

PEG Sohds 1.01 1.12 0.66

Brighteners 0.17 0.17 0.11

DTPA - - 0.70

Sulfate 5.46 6.64 4.25

DC- 1400 Deaerant 0.02 0.02 0.02

Moisture 3.73 3.98 4.33

Minors 0.31 0.49 0.31

B.O.T. Spray-on

Nonionic surfactant 0.50 0.50 0.50 Agglomerate Components

LAS/AS (25/75) 1 1.70 9 60 10.47

Alumino silicate 13.73 1 1.26 12.28

Carbonate 8.11 6.66 7 26

PEG 4000 0.59 0.48 0.52

Moisture/Minors 4.88 4.00 4.36

Functional Additives

Sodium carbonate 7.37 6.98 7.45

Perborate 1.03 1.03 2.56

AC Base Coating - 1.00 -

NOBS - - 2.40

Soil release polymer 0.41 0.41 0.31

Cellulase 0.33 0.33 0.24

Protease¹ 0.1 0.05 0.15

AE-Flake 0.40 0.40 0.29

Liquid Spray-on

Perfume 0.42 0.42 0.42

Noionic spray-on 1.00 1.00 0.50

Minors Up to 100

Example 35

Granular Fabnc Cleaning Composition

Example 36 Granular Fabnc Cleaning Composition

Example 37 The following granular laundry detergent compositions 37 A-C are of particular utility under European machine wash conditions were prepared in accord with the invention:

Example 38 The following formulations are examples of compositions in accordance with the invention, which may be in the form of granules or in the form of a tablet.

Example 39 Granular laundry detergent compositions 39 A-E are of particular utility under Japanese machine wash conditions and are prepared in accordance with the invention:

Liquid Fabric Cleaning Compositions

Liquid fabric cleaning compositions of the present invention preferably comprise an effective amount of one or more protease enzymes, preferably from about 0.0001% to about 10%, more preferably from about 0.001% to about 1%, and most preferably from about 0.001% to about 0.1% by weight of active protease enzyme of the composition. (See U.S. Patent No. 5,679,630 Examples).

Example 40 Liquid Fabric Cleaning Compositions

Example No.

Component A B C D

Protease¹ 0.05 0.03 0.30 0.03 0.10

Protease^" - - - 0.1 0.20

Ci 2- Cj4 alkyl sulfate, Na 20.00 20.00 20.00 20.00 20.00

2-Butyl octanoic acid 5.00 5.00 5.00 5.00 5.00

Sodium citrate 1.00 1.00 1.00 1.00 1.00

Cjø alcohol ethoxylate (3) 13.00 13.00 13.00 13.00 13.00

Monethanolamine 2.50 2.50 2.50 2.50 2.50

Water/propvlene glycol/ethanol ( 100: 1: 1) balance to 100%

In Examples 40 D and E, any combination of the protease enzymes useful in the present invention recited herein, among others, are substituted for Protease¹ and Protease², with substantially similar results.

Examples 41 Liquid Fabric Cleaning Compositions Example No.

Component A B

Ci 2_14 alkenyl succinic acid 3.0 8.0

Citric acid monohydrate 10.0 15.0

Sodium C i2- 15 alkyl sulfate 8.0 8.0

Sodium sulfate of C 12.15 alcohol 2 times ethoxylated - 3.0

C12- 5 alcohol 7 times ethoxylated _ 8.0

Diethylene triamine penta (methylene phosphonic acid) 0.2

Oleic acid 1 8

Ethanol 4.0 4.0

Propanediol 2.0 2.0

Protease¹ 0.01 0.02

Polyvinyl pyrrohdone 1.0 2.0

Suds suppressor 0.15 0.15

NaOH up to pH 7.5

Perborate 0.5 1

Phenol sulphonate 0.1 0.2

Peroxidase 0.4 0.1

Waters and minors up to 100 %

Example 42

Liquid Fabric Cleaning Compositi ons

Example No.

Component 4Q

NaLAS (100%am) 16

Neodol 21.5

Citrate 6.8

EDDS 1.2

Dispersant 1.3

Perborate 12

Phenolsulfonate ester of N-i ιonanoyl-6-amιnocaproιc acid 6

Protease¹ (% pure enzyme) 0.03

Amylase 0.40

Cellulase 0.03

Solvent (BPP) 18.5

Polymer 0.1

Carbonate 10

FWA 15 0.2

Tι0₂ 0.5

PEG 8000 0.4

Perfume 1.0-1.2 Suds suppressor 0.06

Waters and minors up to 100%

Example 43

Liquid Fabric Cleaning Compositions

Example No.

Component A B

D1 H₂0 38.63 -

MEA 0.48 9.0

NaOH 4.40 1.0

Pdiol 4.00 10.0

Citric acid 2.50 2.0

Sodium sulfate 1.75 -

DTPA 0.50 1.0

FWA Premix (Br 15/MEA/Nl 23-9) 0.15 0.15

Na C25AE1.80S 23.50 -

AE3S (H) - 4.0

C11.8HLAS 3.00 14.0

Neodol 2.00 6.0

EtOH 0.50 2.0

Ca*Formate 0.10 0.1

Borax premix (Borax/MEA/Pdiol/CitncAcid) 2.50 -

Boric acid - 1.0

CIO APA 1.50 -

TEPA 105 1.20 -

FA C12-18 5.00 -

Neptune LC 0.50 -

Dye 0.0040 0.0015

Cellulase 0.053 0.2

Amylase 0.15 0.2

Protease¹ 0.1 0.1

DC 2-3597 0.12 0.2

Rapeseed FA 6.50 4.0

Waters and minors up to 100 % Example 44

Liquid Fabric Cleaning Composition

Component 44

NaOH 5.50

Pdiol 6.90

Citric acid 1.50

DTPA 1.50

FWA Premix (Br 15/MEA/Nl 23-9) 0.15

AE3S (H) 2.50

LAS (H) 13.0 Neodol 2.00

EtOH 3.50

Ca*Formate 0.10

Boric acid 1.00

Clay 4.00

Amylase 0.15 Protease¹ 0.02

Fatty Acid 16.50

Waters and minors up to 100 %

Example 45

Liquid Fabric Cleaning Composition

Liquid fabric cleaning composition of particular utility under Japanese machine wash conditions is prepared in accordance with the invention:

Example 46 Liquid Fabric Cleaning Composition Liquid fabric cleaning composition of particular utility under Japanese machine wash conditions and for fine fabrics is prepared in accordance with the invention:

Bar Fabnc Cleaning Compositions

Bar fabnc cleaning compositions of the present invention suitable for handwashmg soiled fabπcs typically contain an effective amount of one or more protease enzymes, preferably from about 0.001% to about 10%, more preferably from about 0.01% to about 1% by weight active protease enzyme of the composition. (See U.S. Patent No. 5,679,630 Examples). Example 47 Bar Fabric Cleaning Compositions

Example No

Component A B C D

Protease¹ 0 3 - 0.1 0.02 Protease² - - 0.4 0.1 C 2-C 6 alkyl sulfate, Na 20 0 20.0 20.0 20.00

C 2-Ci4 N-methyl glucamide 5.0 5.0 5.0 5.00

C_j "C 3 alkyl benzene sulfonate, Na 10.0 10.0 10.0 10.00

Sodium pyrophosphate 7 0 7.0 7.0 7.00 Sodium tnpolyphosphate 7.0 7.0 7.0 7.00 Zeolite A (0.1 -.10μ) 5.0 5.0 5.0 5.00 Carboxymethylcellulose 0.2 0.2 0.2 0.20 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.20 Coconut monethanolamide 5.0 5.0 5.0 5.00 Brightener, perfume 0.2 0.2 0.2 0.20 CaS0₄ 1.0 1.0 1.0 1.00

MgS0₄ 1.0 1.0 1.0 1.00

Water 4.0 4.0 4.0 4.00

Filler* balance to 100%

*Can be selected from convenient matenals such as CaCθ3, talc, clay, silicates, and the like.

In Examples 47 C and D any combination of the protease enzymes useful m the present invention recited herein, among others, are substituted for Protease¹ and Protease², with substantially similar results.

While particular embodiments of the subject invention have been described, it will be obvious to those skilled in the art that various changes and modifications of the subject invention can be made without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all such modifications that are within the scope of the invention. The compositions of the present invention can be suitably prepared by any process chosen by the formulator, non-limiting examples of which are described in U.S. 5,691,297 Nassano et al, issued November 11, 1997; U.S. 5,574,005 Welch et al, issued November 12, 1996; U.S. 5,569,645 Dinniwell et al, issued October 29, 1996; U.S. 5,565,422 Del Greco et al, issued October 15, 1996; U.S. 5,516,448 Capeci et al., issued May 14, 1996; U.S. 5,489,392 Capeci et al., issued February 6, 1996; U.S. 5,486,303 Capeci et al, issued January 23, 1996 all of which are incorporated herein by reference.

In addition to the above examples, the compositions of the present invention can be formulated into any suitable laundry detergent composition, non-limiting examples of which are described in U.S. 5,679,630 Baeck et al., issued October 21, 1997; U.S. 5,565,145 Watson et al., issued October 15, 1996; U.S. 5,478,489 Fredj et al., issued December 26, 1995; U.S. 5,470,507 Fredj et al., issued November 28, 1995; U.S. 5,466,802 Panandiker et al., issued November 14, 1995; U.S. 5,460,752 Fredj et al., issued October 24, 1995; U.S. 5,458,810 Fredj et al., issued October 17, 1995; U.S. 5,458,809 Fredj et al., issued October 17, 1995; U.S. 5,288,431 Huber et al., issued February 22, 1994 all of which are incorporated herein by reference.

Having described the invention in detail with reference to prefeoed embodiments and the examples, it will be clear to those skilled in the art that various changes and modifications may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

WHAT IS CLAIMED IS:

1. A method for reducing fabric damage to laundered fabric that is subjected to multiple wash cycles, the method comprising selecting a treating composition that provides from 100 ppm to 2500 ppm, preferably to 1700 ppm, of an organic surfactant to an aqueous wash solution and contacting said fabric with said wash solution such that the fabric damage of said treated fabric is less than the fabric damage to a fabric that is treated with an aqueous wash solution having no or lower level of surfactant.

2. The method according to Claim 1 wherein said treating composition further comprises additional cleaning adjunct materials selected from the group consisting of bleaching agents, builders, alkalinity sources, and mixtures thereof.

3. The method according to Claim 1 or 2 wherein said treating composition further comprises additional cleaning adjunct materials selected from the group consisting of enzymes, chelants, soil releasing agents, dye transfer inhibiting agents, fabric softening agents, and mixtures thereof.

4. The method according to any of Claims 1 to 3 wherein said treating composition is added to a twin tub washing machine to provide from 100 ppm to 300 ppm of said organic surfactant.

5. The method according to any of Claims 1 to 3 wherein said treating composition is added to a vertical axis washing machine to provide from 200 ppm to 1000 ppm of said organic surfactant, preferably from 300 ppm to 900 ppm.

6. The method according to any of Claims 1 to 3 wherein said treating composition is added to an horizontal axis washing machine to provide from 800 ppm to 2500 ppm of said organic surfactant, preferably from 900 ppm to 1700 ppm.

7. The method according to any of Claims 1 to 6 wherein said fabric is made from natural fibers, preferably selected from the group consisting of cotton, rayon and Lyocell.

8. The method according to any of Claims 1 to 7 wherein said treating composition is selected from the group consisting of granular, paste, gel or liquid laundry detergent composition.

9. An article of manufacture comprising a detergent composition comprising a high level of surfactant packaged in a container in association with instructions to use the composition at a level that will provide from 100 ppm to 2500 ppm, preferably to 1700 ppm, of an organic surfactant in the aqueous wash solution to provide the benefit that fabric damage is reduced as compared to a comparable treatment with lower level of, or no, surfactant.

10. The article of manufacture according to Claim 9 wherein said detergent composition further comprises additional cleaning adjunct materials selected from the group consisting of bleaching agents, builders, alkalinity sources, and mixtures thereof.

11. The article of manufacture according to Claim 9 or 10 wherein said detergent composition further comprises additional cleaning adjunct materials selected from the group consisting of enzymes, chelants, soil releasing agents, dye transfer inhibiting agents, fabric softening agents, and mixtures thereof.

12. The article of manufacture according to any of Claims 9 to 11 wherein said detergent composition is selected from the group consisting of granular, paste, gel or liquid laundry detergent composition.

13. The article of manufacture according to any of Claims 9 to 12 wherein said detergent composition is added to a twin tub washing machine to provide from 100 ppm to 300 ppm of said organic surfactant.

14. The article of manufacture according to any of Claims 9 to 12 wherein said detergent composition is added to a vertical axis washing machine to provide from 200 ppm to 1000 ppm of said organic surfactant.

15. The article of manufacture according to Claim 14 wherein said detergent composition is added to provide from 300 ppm to 900 ppm of said organic surfactant.

16. The article of manufacture according to any of Claims 9 to 12 wherein said detergent composition is added to an horizontal axis washing machine to provide from 800 ppm to 2500 ppm of said organic surfactant.

17. The article of manufacture according to Claim 16 wherein said detergent composition is added to provide from 900 ppm to 1700 ppm of said organic surfactant.

18. The article of manufacture according to any of Claims 9 to 17 wherein said fabric is made from natural fibers, preferably selected from the group consisting of cotton, rayon and Lyocell.