EP1093512A2 - Methods for reducing or preventing the degradation of rubber in domestic bleach processes - Google Patents

Abstract

The present invention relates to methods for reducing or preventing the degradation of rubber in domestic bleach processes, and more particularly to methods of cleaning fabrics in an automatic washing machine.

Description

METHODS FOR REDUCING OR PREVENTING THE DEGRADATION OF RUBBER IN DOMESTIC BLEACH PROCESSES

TECHNICAL FIELD

The present invention relates to methods for reducing or preventing the degradation of rubber, especially natural rubber, in domestic bleach processes, and more particularly to methods of cleaning fabrics in an automatic washing machine. BACKGROUND OF THE INVENTION It has long been known that peroxygen bleaches are effective for stain and/or soil removal from fabrics, but such bleaches are temperature dependent. At a wash liquor temperature of 60° C, peroxygen bleaches become relatively ineffective. As a consequence, there has been substantial amount of industrial research to develop bleaching systems which contain an activator that renders peroxygen bleaches effective at wash liquor temperatures below 60° C.

Numerous substances have been disclosed in the art as effective bleach activators. One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on dingy, yellow stains such as those resulting from body oils. Another type of activators, such as those activators which generally comprise long chain alkyl moieties, are hydrophobic in nature and provides excellent performance on dingy stains. However, many of the hydrophobic activators developed thus far can promote damage to rubber parts used in certain washing machines. Because of these negative effects on washing machine parts, particularly natural rubber, the selection of detergent-added bleaching systems has long been limited. This is especially true for European detergent/bleaches, since many washing machines manufactured in Europe have been equipped with key parts, such as sump hoses, door seals and motor gaskets, made of rubber. A need, therefore, exists for a bleaching system which provides dingy soil clean up without substantially damaging the rubber parts found in washing machines.

The search, therefore, continues for more effective bleach materials, especially for ones which do not substantially damage the rubber parts found in washing machines. Improved bleach materials should be safe, effective, and will preferably be designed to interact with troublesome soils and stains. Various activators have been described in the literature. Many are esoteric and expensive. This need remains, to find a bleach material which is effective on all soils, can operate in all conditions and is cost effective without substantially damaging the rubber parts found in washing machines.

BACKGROUND ART U.S. Patents 5,438,147 , 5,061,807, European Patents 0 325 288 Al, 0 325 289 A 1, 0 366 041 A2, German Patent Application DE 3 823 172 A2 and Japanese Patent Application JP 4-28799 all disclose various imidopercarboxylic acid bleach activators. U.S. Patent 5,132,431 discloses a process for the continuous preparation of imidoperoxycarboxylic acids. European Patent 0 484 095 A2 discloses imidoperoxycarboxylic acids in detergent compositions. U.S. Patent 5,419,846 discloses imidoperoxycarboxylic acids encapsulated in granules. European Patent 0 435 379 A2 discloses suspended compositions containing imidoperoxycarboxylic acids. PCT application WO 94/28104 Al disclosed amino-derived bleach activators which do not damage natural rubber parts of washing machines.

SUMMARY OF THE INVENTION It has now been found that certain bleach materials are effective in removing soils and stains from fabrics and hard surfaces such as dishes as well as minimizing the degradation of rubber in domestic bleaching processes. The bleach materials are designed to function over a wide range of washing or soaking temperatures and are compatible with rubber surfaces, such as those of sump hoses, door seals and motor gaskets used in washing machines. In short, domestic bleaching processes herein provide a substantial advantage over those known in the art, as will be seen from the disclosures hereinafter.

In accordance with a first aspect of the present invention, a method of reducing or preventing degradation of rubber, in a domestic bleaching process is provide for. This method involves the steps of contacting a substrate comprising rubber with a detergent composition including a bleach additive selected from the group consisting of:

(a)

(b)

(c)

(d)

(e)

; and

(f) mixtures thereof; wherein, any of said moieties, A, E and X comprise substituted or unsubstituted, branched or linear hydrocarbyl groups; M is selected from hydrogen and compatible cations having a charge q; and y and z are integers such that the compound is electrically neutral; and L is a leaving group or OH.

In accordance with a second aspect of the present invention, a method for cleaning fabrics in an automatic washing machine having parts made of rubber which is susceptible to oxidative degradation is provided. This method involves the steps of agitating the fabrics in the washing machine in an aqueous liquor comprising a bleach additive selected from the group consisting of: (a)

(b)

(c)

(d)

(e)

and

(f) mixtures thereof; wherein, any of said moieties, A, E and X comprise substituted or unsubstituted, branched or linear hydrocarbyl groups, M is selected from hydrogen and compatible cations having a charge q; and y and z are integers such that said compound is electrically neutral; and L is a leaving group or OH; and such that said rubber parts of said machine are substantially undamaged by the bleaching system.

The methods of the present invention are ideally suited for use in laundry applications and automatic dishwashing applications. Bleach additives are intended to be employed in conjunction with a source of hydrogen peroxide such as a bleaching composition or a bleaching composition including a detergent. Accordingly, the compositions used in the method of the present invention when used in laundry applications may also include additives, such as hydrogen peroxide source, detersive surfactants, chelates, and detersive enzymes. The compositions are preferably employed at concentrations of at least about 50 ppm and typically from about 1,000 to about 10,000 ppm in solution. The water temperatures preferably range from about 25°C to about 50°C. The water to fabric ratio is preferably from about 1 : 1 to about 15:1 Methods for washing soiled dishes such as tableware, also involve contacting the soiled dishes with an aqueous dishwashing liquor. The dishwashing liquor includes the bleach additive as fully described above. The dishwashing liquor may also include additives, such as a hydrogen peroxide source, detersive surfactants, chelates, and detersive enzymes. The compositions are preferably employed at concentrations of at least about 50 ppm and typically from about 1,000 to about 10,000 ppm in solution. The water temperatures preferably range from about 25°C to about 50°C.

Accordingly, it is an aspect of the present invention to provide methods for reducing or preventing degradation of rubber, in a domestic bleaching process using a bleach additive. It is another aspect of the present invention to provide a method for washing fabrics using these same bleach additives. These, and other, aspect, features and advantages will be clear from the following detailed description and the 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 PREFERRED EMBODIMENTS The present invention relates to method of reducing or preventing degradation of rubber, in a domestic bleaching process with a composition which contain a bleach additive. The bleach additive used in the present invention is represented by the formulas: (a)

(b)

(C)

⁰ ff

A A N-X— C ll— OO—C ll—X — N A v

O ii A o

(d)

(e)

and

(f) mixtures thereof; wherein X is an substituted or unsubstituted, branched or linear hydrocarbyl group and when more than one X is present, each X can be the same or different. Preferably X is an unsubstituted hyrocarbyl, more preferably X is selected from substituted or unsubstituted, branched or linear Cl -C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkylene. Preferably, X is branched or linear C^ -C12 alkyl, branched or linear C2 -Cj2 alkylene, more preferably branched or linear Ci -Cg alkyl, branched or linear C2-Cg alkylene, most preferably linear Ci -Cg alkyl. E is an substituted or unsubstituted, branched or linear hydrocarbyl group, and each E can be the same or different. That is, when present, E and X or A and X can be selected in such a fashion as to produce molecules which are symmetric or asymmetric across any axis. Preferably E is selected from the group consisting of substituted or unsubstituted, branched or linear C1-C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted, branched or linear alkylaryl. It is even more preferred that each E has at least 6 carbon atoms. A is an substituted or unsubstituted, branched or linear hydrocarbyl group and when more than one A is present, each A can be the same or different. Preferably A is selected from

Rl

; more preferably A is selected from: 1 I , j

^R\ CH-(CH₂)_n-CH ^R _R __c_ ti__R ^{4 X} or / \ . wherein n is selected from the numbers 0, 1, 2, 3 or 4. Preferably, n is 0,1,2 or 3 and more preferably, 0,1, or 2. Ri is selected from the group consisting of hydrogen, chloride, bromide, iodide, substituted or unsubstituted branched or linear C1-C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. Ri is preferably hydrogen, chloride, substituted or unsubstituted branched or linear Cj- Cjg alkyl, substituted or unsubstituted branched or linear C2-C^g alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. More preferably, R^ is hydrogen, unsubstituted branched or linear Cj-Ci g alkyl, unsubstituted branched or linear C2-C1 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl and substituted or unsubstituted alkylnapthyl.

R2 is selected from the group consisting of hydrogen, chloride, bromide, iodide, SO3M_zq⁺, SO4M_z ⁺, COOM_zq⁺, substituted or unsubstituted branched or linear Ci -C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. R^ is preferably hydrogen, chloride, substituted or unsubstituted branched or linear C\- Cj alkyl, substituted or unsubstituted branched or linear C2-Cι alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. More preferably, R^ is hydrogen, unsubstituted branched or linear Cj-Ci g alkyl, unsubstituted branched or linear C2-C16 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl and substituted or unsubstituted alkylnapthyl. It is further preferred that one of R and R2 is hydrogen or unsubstituted branched or linear Ci -Cg alkyl and the other is either an unsubstituted branched or linear Cj-Cjg alkyl or an unsubstituted branched or linear C2-C16 alkenyl.

R3 and R^ are independently selected from hydrogen and Ci -Cg substituted or unsubstituted branched or linear alkyl. Preferably R^ and R^ are independently selected from hydrogen and C1 -C3 substituted or unsubstituted branched or linear alkyl.

M is selected from hydrogen and compatible cations having a charge q; y and z are integers such that the bleach additive is electrically neutral. Preferably, M is hydrogen or a cation which provides solubility to the bleach activator, selected from an alkali metal, an alkaline earth metal, ammonium or substituted ammonium cation, with sodium, potassium and Magnesium being most preferred, y and z are integers which are selected such that the overall charge of the molecule is zero. The preferred bleach additive is selected from:

, or mixtures thereof; wherein m is an integer selected from the range 1 to 14, preferably 1 to 12, more preferably 1 to 8, most preferably 1 to 5. R* is selected from the group consisting of hydrogen, chloride, bromide, iodide, substituted or unsubstituted branched or linear Cj-C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. Rl is preferably hydrogen, chloride, substituted or unsubstituted branched or linear Cj- Cjg alkyl, substituted or unsubstituted branched or linear C2-Cι g alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. More preferably, Ri is hydrogen, unsubstituted branched or linear C^-Cjg alkyl, unsubstituted branched or linear C2-C16 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl and substituted or unsubstituted alkylnapthyl.

R2 is selected from the group consisting of hydrogen, chloride, bromide, iodide, SU3M_z ⁺, SO4M_zq⁺, COOM_zq⁺, substituted or unsubstituted branched or linear Ci -C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. R^ is preferably hydrogen, chloride, substituted or unsubstituted branched or linear C1 - Ci g alkyl, substituted or unsubstituted branched or linear C2-Cι alkenyl, substituted or unsubstituted aryl and substituted or unsubstituted alkylaryl. More preferably, R^ is hydrogen, unsubstituted branched or linear Cj-Cjg alkyl, unsubstituted branched or linear C2-C16 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted napthyl, substituted or unsubstituted alkylphenyl and substituted or unsubstituted alkylnapthyl. It is further preferred that one of R^ and R2 is hydrogen or unsubstituted branched or linear C_j-Cg alkyl and the other is either an unsubstituted branched or linear Ci -Cjg alkyl or an unsubstituted branched or linear C2-Cjg alkenyl.

L is a leaving group or OH. A leaving group is any group that can be displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the peroxycarboxylic acid. Generally, for a group to be suitable leaving group it must exert an electron attracting effect. It should also form a stable entity so that the rate of the back reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion. The leaving group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g. a wash cycle). However, if the leaving group is too reactive, this activator will be difficult to stabilize for use in a bleaching composition. These characteristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11. Preferred leaving groups are those selected from the group consisting of:

and mixtures thereof.

Wherein R , R? and R^ maybe the same or different, and are selected from H, alkyl, alkaryl, aryl or aralkyl containing from about 1 to about 14 carbon atoms, halogen, hydroxyl, C\ to C14 alkoxyl, amino, C\ to C14 alkylamino, COOR^ ( wherein R^ is H or C\ to C14 alkyl) and carbonyl functions. Y is H or a solubilizing group.

The preferred solubilizing groups are -SO3" M⁺ , -CO2"M⁺, -SO4^"M⁺, -

N⁺(R6)4X" and -0-N(R^)3. Most preferably the solubilizing groups are -SO3" M⁺ and -CO2"M⁺, with R^ as hereinbefore defined. M is a cation which provides solubility to bleach activator and X is an anion which provides solubility to bleach activator. Preferably, M is an alkali metal, alkaline earth metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred.

Preferably, the anion X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleaching solution in order to assist in their dissolution.

L can also be a modified or unmodified lactam leaving group. The lactams which are suitable as leaving groups in the present application have the generic structure:

where R represents an optionally substituted alkenyl chain with at least two carbon atoms in the alkenyl chain. This alkenyl chain forms a cyclic structure with the -N- and -C(O)-. The term modified means that the alkenyl can be substituted at least once or that one or more of the alkenyl carbon atoms can be substituted by a suitable heterocycle or any combination of both. Suitable heterocyclic chain substitutes are O, N, and S, with O being preferred. Suitable substituents include, but are not limited to, Ci -Cg alkyl, Cj-Cg alkenyl, Cj-Cg alkoxy, chloride, bromide, iodide. The preferred substituents are Ci -Cg alkyl, Cj-Cg alkoxy and chloride. The most preferred modified lactam leaving groups are: alpha-chlorocaprolactam, alpha- chloro-valerolactam, alpha,alpha-dichlorolactam, alpha,alpha-dichlorovalerolactam, alpha-methoxycaprolactam, alpha-methoxy-valerolactam,

and mixtures thereof.

When the lactams are unmodified, it means that they contain no substituents other hydrogen and have no heterocyclic substitution of the alkenyl chain of R. R is preferably an alkenyl chain of two to seven carbon atoms. It is preferred that the lactam leaving group will be unmodified. It is more preferred that the unsubstituted lactam leaving group will be either caprolactam or valerolactam. That is:

The amount or physical form of the bleach additive used in the various methods of the present invention varies. Typically the bleach additive will be used in amounts of 0.1% to about 99.9%, preferably about 0.1% to about 60%, more preferably about 0.1% to about 40%, even more preferably, still, about 0.1% to about 30%. Preparation of the bleach additive: The bleach additive of the present application can be made via any of the well known synthesis methods. The bleach additive of formulas (a), (b) and (d) can be made by reacting the appropriate anhydride, either cyclic or acyclic, with an amino acid of the formula H2N-X-COOH. This reaction is typically done in an inert atmosphere. See US Patents 5,061,807 (Gethoffer et al) and 5,438,147 (Jaekel et al), and EP 349,940 all of which are incorporated herein by reference. Alternatively, these bleach additive, namely (a), (b) and (d), can be prepared by using an inexpensive lactam instead of the amino acid. Typically, the reaction involving lactams is under an inert atmosphere, for 2 to 20 hours at a temperature of 100° to 250°C. The resulting imidocarboxylic acids obtained by either method can then be reacted with hydrogen peroxide in the presence of a strong acid to form the bleach act additive ivator of formula (b). See US Patent 5,061,807 (Gethoffer et al) and Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), Volume XI/2, page 17.

A method for the continuos production of imidoperoxycarboxylic acid can be found in US Patent 5,132,431 (Fuchs et al).

The production of bleach additive of formula (a) when L is a leaving group can be done by starting with the imidocarboxylic acid and refluxing it with an hydroxybenzenederivative, which then becomes the desired leaving group, in an inert atmosphere. Preparation methods of this type are described, for example in EP 105,627, EP 105,673 and DE 3,824,901. Other synthesis processes are described in EP 202,698, EP 210,674, EP 140,251, EP 163,224, EP 163,225, EP 125,641, EP 165,480, EP 211,045, EP 120,591, EP 166,571, EP 204,116, EP 153,222, EP 153,223, EP 164,786, EP 201,222, EP 227,194, EP 207,445, EP 220,656 and EP 229,890, all of which are incorporated herein by reference. Alternatively, there is a two step process which involves converting the acid to the corresponding acid halide, preferably acid chloride, in a known manner. Then in the second step the acid halide is reacted with a hydroxy form of the desired leaving group, or hydroxy leaving group. In this reaction the acid halide and hydroxy leaving group are reacted in the ratio of 0.1-2.5:1, preferably 0.5-1.5:1, in an inert high-boiling solvent, for example toluene or xylene, at temperature of between 80°-200°C, preferably at 100°-150°C. The reaction time is typically between 60 and 360 minutes, but it can be longer depending upon the reactivity of the acid halide. After the reaction mixture has cooled, the solvent is filtered off with suction and the filter cake is washed and/or recrystallized from a suitable solvent. See Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry), Volume E5, p. 593-600 and US Patent 5,438,147 (Jaekel et al), both of which are incorporated herein by reference. Analogous reactions are described in the Patent applications EP 98,129, EP 148,148, EP 164,786 and EP 220,826.

Other methods can be found in "New developments in the field of Imidoperoxicarboxylic acids", by H. Gethoeffer et al, a paper presented at the 1990 AOCS meeting, Baltimore, MD, EP patent application 366,041 and Japanese Laid- open Patent application (Kokai) No 4-28799. Bleach additive of formulas (c) and (e) can be made by either reacting the corresponding acyl chloride with sodium peroxide or hydrogen peroxide. Alternatively, the acid anhydride may be used in place of the acyl chloride. To form unsymetrical compounds the acyl chloride or acyl anhydride is reacted with peroxycarboxylic acid. These and other alternative synthesis methods are found in R. Hiatt in Organic Peroxides, (Ed. Dr. D. Swern), Vol. II, Wiley-Interscience, New York-London, 1970; pp. 779-930 and G. Bouillon et al., The chemistry of peroxides, (Ed. Saul Patai), John Wiley & sons, Chichester-New York-Brisbane-Toronto- Singapore, 1983; pp. 279-309, both of which are incorporated herein by reference. Alternative preparations of the bleach additive of formulas (c) and (e) can be found in European patent applications 484,095, 325,289 and 325,288, all of which are incorporated herein by reference. Synthesis Examples: 1(a). Preparation of C8 saturated imido acid from octyl succinic anhydride and 6- aminocaproic acid.

A two liter 3 -neck round-bottomed flask equipped with mechanical stirring, reflux condenser and Dean-Stark apparatus is charged with 159.2 g (0.75 mol) octyl succinic anhydride, 108.2 g (0.825 mol) 6-aminocaproic acid and 750 ml toluene (1 L toluene/1 mol succinic anhydride). Under argon and with stirring, the reaction is heated to toluene reflux (130-140°C). To this is added 10.5 ml (0.075 mol, 7.6 g) triethylamine. The condenser and Dean- Stark apparatus is wrapped with glass wool to facilitate reflux. The reaction is heated and stirred for 4 hours or until water collection slows considerably or stops. Thirteen milliliters of water is collected (96% of theory). The reaction is transferred to a 2 L 1-neck round-bottomed flask and the toluene is removed at 40°C on the rotary evaporator. The reaction is cooled to room temperature before placing in the freezer to solidify. The solids are broken apart into large chunks before 1.5 L water containing 15 ml cone. HC1 (2 L water/1 mol theoretical product, containing 10 ml cone. HCl/1 L water) is added. The reaction is stirred mechanically for several hours. The product is collected by filtration and dried under vacuum at 50°C for 16 hours. The crude recovery is 254.5 g. The sample is purified by heating the crude product in 1 L 95% ethanol, filtering hot to remove insoluble material, cooling to room temperature, then storing in the freezer to recrystallize. The final product is collected by vacuum filtration then allowed to air dry. Recovery is 177.4 g (73% of theory). Analysis by gas chromatography yields 99.7% activity.

Kb). Preparation of the phenol sulfonate ester of the imido acid from octyl succinic anhydride and 6-aminocaproic acid. A 500 ml 3 -neck round-bottomed flask is equipped with mechanical stirring, reflux condenser and Dean-Stark apparatus. The flask is charged with 60.2 g (0.185 mol) C8 saturated imido acid (prepared above). The flask is heated in an oil bath, under argon, to 190°C (the imido acid melts). To this is added 44.1 g (0.185 mol) acetoxybenzenesulfonate, 3.6 g (0.06 mol) imidazole and 0.8 g (0.01 mol) sodium acetate. As the reaction becomes viscous, tetramethylene sulfone is added to maintain stirring. A total of 20 ml tetramethylene sulfone is added. The reaction is shut down after 5 hours and cooled to room temperature. A water/ice bath is used to facilitate cooling. Once at room temperature, 300 ml of 10% aqueous sodium chloride solution is added and the reaction is stirred mechanically to break apart the solids. The product is transferred to a 1 L Erlenmeyer flask. With magnetic stirring, an additional 400 ml of 10% aqueous sodium chloride solution is added. The mixture is stored cold overnight. The product is centrifuged at 25,000 rpm for 30 minutes at 25°C using a Beckman Model L-8-80 Ultracentrifuge. The collected solids are rinsed with 300 ml of 10% aqueous sodium chloride solution and centrifuged a second time under the same conditions. The collected solids are dried under vacuum at 50°C overnight then ground to a fine powder recovering 57.9 g (62%) of theory). The product is submitted for analysis by NMR and HPLC. By HPLC, the product is 68% active, with the main impurity being 25% C8 saturated imido acid starting material. To remove the imido acid, the product is slurried in 100 ml acetone, collected by filtration and dried under vacuum at 50°C overnight. Final product recovery was 40 g (43% of theory). Analysis by HPLC yields an activity of 94.8% with 1.2% imido acid, 0.3% acetoxybenzenesulfonate and 0.2% sodium phenol sulfonate. 2(a). Preparation of C12 unsaturated imido acid from dodecenyl succinic anhydride and 6-aminocaproic acid.

A one liter 3-neck round-bottomed flask equipped with mechanical stirring, reflux condenser and Dean-Stark apparatus is charged with 53.3 g (0.20 mol) dodecenyl succinic anhydride, 26.2 g (0.20 mol) 6-aminocaproic acid, 2.8 ml (0.02 mol, 2.0 g) triethylamine and 300 ml toluene (1.5 L toluene/1 mol succinic anhydride). Under argon and with stirring, the reaction is heated to toluene reflux (130-140°C). The condenser and Dean-Stark apparatus is wrapped with glass wool to facilitate reflux. The reaction is heated and stirred for 4 hours or until water collection had slows considerably or stops. There is 3.4 ml of water collected (94% of theory). The reaction is transferred to a 1 L 1-neck round-bottomed flask and the toluene is removed at 40°C on the rotary evaporator then cooled to room temperature. To this is added 400 ml water containing 4 ml cone. HC1 (2 L water/1 mol theoretical product, containing 10 ml cone. HCl/1 L water). The reaction is stirred mechanically for several hours. The reaction is stored cold overnight then the water is decanted. The product is dried under vacuum at 60°C for 16 hours. The crude recovery is 73.4 g (96% of theory). Analysis by ^H NMR (CDCI3 solvent) indicates the material is the desired product.

2(b). Preparation of the phenol sulfonate ester of the imido acid from dodecenyl succinic anhydride and 6-aminocaproic acid.

A 500 ml 3 -neck round-bottomed flask is equipped with mechanical stirring, reflux condenser and Dean-Stark apparatus. The flask is charged with 60.7 g (0.16 mol) C12 unsaturated imido acid (prepared above). The flask is heated in an oil bath, under argon purge, until the imido acid melted. To this is added 38.1 g (0.16 mol) acetoxybenzenesulfonate, 3.1 g (0.05 mol) imidazole and 0.7 g (0.01 mol) sodium acetate. The reaction is heated to 170-180°C with good stirring. As the reaction became viscous, tetramethylene sulfone is added to maintain stirring. A total of 35 ml tetramethylene sulfone is added. The reaction is shut down after 4 hours and cooled to room temperature overnight. The product is triturated in acetone, collected by filtration and dried under vacuum at 50°C for 16 hours. Final product recovery is 65.8 g (74% of theory). Analysis by proton NMR (deuterated methyl sulfoxide solvent) indicates the material is the desired product. The activity of the product is determined to be 93%) relative to the residual phenol sulfonate peaks on the spectrum. Example 3. N-Nonanoylsuccinimide

20g of succinimide is suspended in 100 ml pyridine, 0.5g N,N- dimethylaminopyridine is added, and 39.2g nonanoic acid chloride is added dropwise at ice-bath temperatures. Subsequently, the mixture is stirred for one hour at room temperature and 500 ml of a 2M HC1 solution is added with cooling. The aqueous phase is extracted with ethyl acetate and the organic phase is washed with a 2M HC1 solution and dried (Na2SO4). After removing the solvent, the residue is then recrystallized twice from n-hexane. 31.6g (65%) of N-nonanoylsuccinimide is obtained as a colorless solid. Melting point: 59 to 60°C. (n-hexane). Example 4

(i)ω-Phthalimidobutanoic acid 75.04g (0.5 mol) of phthalic anhydride, 43.55g (0.5 mol) of γ-pyrrolidone and 9g of water are reacted in an autoclave for 5 hours at 180°C. under 3 bar of nitrogen. The melt is then poured into a porcelain dish. Yield: 116.2g (99.6%), white crystals, Mpt: 110°-112°C. (iQω-Phthalimidoperoxybutanoic acid

46.6g (0.2 mol) of ω-Phthalimidobutanoic acid is dissolved in 2.5 equivalents of a 80%) solution of sulfuric acid. 2.5 Equivalents of a 42% solution of hydrogen peroxide were added dropwise, while the acid solution is cooled, such that the acid solutions temperature remains between 40° and 45 °C. When the addition is completed, the acid solution is cooled to 25°-30°C and diluted with water and the peracid, which will precipitate, is filtered off with suction . The filter cake is then washed with water and dried at 35°C in a vacuum drying cabinet. Yield: 46.4g (93%>), white crystals, active oxygen content(AO), (determined by iodometric titration): 6.1% (95.3%), Mpt: 102°-106°C Example 5

(i ω-[3-Carboxyphthalimido]hexanoic acid

As per example 4(i) above but, 191.1g (1 mol) of trimellitic anhydride, 113.1g (1 mol) of ε-caprolactam and 18g of water is used and the reaction is at 210°C instead. Yield: 304.1g (100%), white crystals, Mpt: 196°-197°C. (ii)ω-|^~3-Carboxyphthalimido^~|peroxyhexanoic acid

As per example 4(ii) above but, 244.2g (0.8 mol) of ω-[3- Carboxyphthalimidojperoxyhexanoic acid is reacted. Yield: 235g (87%), AO: 4.8% (96%), Mpt: 144°C. Example 6

(i)Pyromellitimido-di-ε-caproic acid

As per example 4(i) above but, 76g (0.35 mol) of pyromellitic anhydride, 79.2g (0.7 mol) of caprolactam and 2g of water is used and the reaction is at 210°C, for 18 hours and under nitrogen pressure of 4 bar instead. Yield: 149g (96%), white crystals, Mpt: 232°C.

(ii)Pyromellitimido-di-ε-percaproic acid

As per example 4(ii) above but, 18g (0.077 mol) of Pyromellitimido-di-ε-percaproic acid is reacted.

Yield: 9g (82%),white crystals, AO: 6.6% (98.5%), Mpt: 139°C. Example 7

Di-ω -Phthalimidoperoxybutanoic acid ω-Phthalimidobutanoyl chloride (25.2g, 0.1 mole) is dissolved in 175ml ether and the mixture cooled to 0°C. Hydrogen peroxide (4.25 g of 60% concentration, 0.075 mole) is added to the reaction flask, followed by dropwise addition of pyridine (9.5g, 0.12mole), while the temperature is maintained at 0-5°C. The diacyl peroxide precipitates as it forms. After the pyridine is completely added, the ice bath is removed and stirring of the slurry is continued for one hour. A homogenous solution is obtained by adding ether, which has been previously cooled to 0-2°C, at room temperature. The ether solution is washed with dilute hydrochloric acid, 5% potassium bicarbonate, followed then by water and is then dried over anhydrous sodium sulfate. The desired product is prepared in 98% yield. Rubber

Rubber as used herein refers to any rubber, both synthetic and natural, preferably natural rubber, which is present in a domestic bleaching process. This includes for example natural rubbers, vulcanized rubbers, vinyl rubbers, silicone rubbers, nitrile rubbers, isoprene rubbers, styrene rubbers and butadiene rubbers. Since it is preferred that the process be performed in an automatic washing machines the rubber is which is typically present in automatic washing machines, for example in door seals, motor gaskets, washers and sump hoses. It is especially preferred that rubber refers to the natural rubber parts, especially the door seals, motor gaskets and sump hoses, present in front loading washing machines, especially those front loading washing machines used or manufactured in Europe. It is also preferred that the rubber be a rubber which is susceptible to oxidative degeneration, for example natural rubber. Domestic Bleaching process

The term "domestic bleaching process", means any process involving bleaching in a domestic environment. For example, it includes, but is not limited to, bleaching fabrics in a basin, sink or bucket, cleaning fabrics in a washing machine, cleaning dishes in an automatic dishwasher, cleaning floors or hard surfaces, etc. Preferably, the domestic bleaching process is performed in a washing machine, more preferably a front loading washing machine. The rubber substrate present in the process can be in a variety of different forms, for example, as door seals, motor gaskets, sump hoses etc., in washing machines, detergent and/or fabric softener dispensers, such as the DOWNY BALL® Procter & Gamble, floor coverings, buckets, basins, sponges, mops, rubber gloves etc. Preferably, the rubber substrate are door seals, motor gaskets, sump hoses present in washing machines.

CONVENTIONAL ADDITIVES Conventional additives can be used in conjunction with the bleach additive in the compositions used in the present method. Typically these conventional additives will be present from about 0.0001% to about 99.999%, preferably about 0.1% to about 99.9%), more preferably about 1% to about 99.9%, even more preferably about 1% to about 80%) by weight. The conventional additives, are any additive which are commonly used in bleach, bleaching additive and detergent compositions. These can be selected from, but not limited to, bleaches, surfactants, builders, fabric softeners, enzymes and bleach catalysts. It would be readily apparent to one of ordinary skill in the art what additives are suitable for inclusion into the compositions. It is also readily apparent that any conventional additive selected is one that is compatible with the rubber components in washing machines. That is, the conventional additive must cause minimal damage, preferably no damage to the rubber components in a washing machine. The list provided herein is by no means exhaustive and should be only taken as examples of suitable additives. It will also be readily apparent to one of ordinary skill in the art to only use those additives which are compatible with the bleach additive and other components in the composition, for example, bleach. Bleaches

The compositions used in the methods of the present invention may also contain a source of hydrogen peroxide. A source of hydrogen peroxide herein is any convenient compound or mixture which under consumer use conditions provides an effective amount of hydrogen peroxide. Levels may vary widely and are typically from about 0.1 % to about 70%, more typically from about 0.2% to about 40% and even more typically from about 0.5% to about 25%, by weight of the compositions herein.

The 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. Mixtures of any convenient hydrogen peroxide sources can also be used. Organic sources of hydrogen peroxide, such as diacyl peroxides, can also be used. 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. Preferred is dibenzoyl peroxide.

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 silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. The source of hydrogen peroxide and cyclic imido activator are typically at a ratio of from about 3:1 to about 20:1, as expressed on a basis of peroxide: activator in units of moles H2O2 delivered by the hydrogen peroxide source to moles bleach activator.

Fully-formulated bleach additive and bleaching compositions, particularly those for use in laundry and automatic dishwashing, typically will also comprise other adjunct ingredients to improve or modify performance. Bleach catalysts

If desired, the compositions used in the present methods can also include a bleach catalyst. 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. Pat. 4,430,243.

Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of theses catalysts include Mn^2(^u"C)3(l,4,7-trimethyl-l,4,7-triazacyclononane)2- (PFg)₂ ("MnTACN"), Mn^πi2(u-O)ι (u-OAc)2(l ,4,7-trimethyl-l ,4,7-triazacyclono- nane)2-(C104)2, Mn^IV4(u-O)g(l ,4,7-triazacyclononane)4-(ClO4)2, Mn^mMn^IV4(u- O) j (u-O Ac)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)3 , and mixtures thereof. See also European patent application publication no. 549,272. Other ligands suitable for use herein include l,5,9-trimethyl-l,5,9-triazacyclododecane, 2- methyl-l,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in automatic dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention. For examples of other suitable bleach catalysts herein see U.S. Pat. 4,246,612, U.S. Pat. 5,227,084 and WO 95/34628, December 21, 1995, the latter relating to particular types of iron catalyst.

See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl-l,4,7-triazacyclononane(OCH3)3_(PFg). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of manganese (II), (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches another useful bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)- cyclic ligand. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co-, Cu-, Mn-, or Fe- bispyridylmethane and bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine- cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2- bispyridylamine)2θ2Clθ4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Other bleach catalyst examples include Mn gluconate, Mn(CF3SO3)2, Co(NH3)5Cl, and the binuclear Mn complexed with tetra-N-dentate and bi-N- dentate ligands, including N4MnIH(u-O)2MnIV 4)⁺and [Bipy2MnM(u- O)₂MnIVbip_y2]-(ClO4)3.

Particularly preferred manganese catalyst for use herein are bridged cyclo Mn catalysts those which are fully disclosed in copending patent applications PCT applications PCT/IB98/00298 (Attorney Docket No. 6527X), PCT/IB98/00299 (Attorney Docket No. 6537), PCT/IB98/00300 (Attorney Docket No. 6525XL&), and PCT/IB98/00302 (Attorney Docket No. 6524L#).

Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

Preferred are cobalt (III) catalysts having the formula: Co[(NH₃)_nM'_mB'_br_tQ_qP_p] Y_y wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (preferably 4 or 5; most preferably 5); M' represents a monodentate ligand; m is an integer from 0 to 5 (preferably 1 or 2; most preferably 1); B' represents a bidentate ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or 1 ; Q is a tetradentate ligand; q is 0 or 1 ; P is a pentadentate ligand; p is 0 or 1 ; and n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counteranions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein further at least one of the coordination sites attached to the cobalt is labile under automatic dishwashing use conditions and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (III) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a normal hydrogen electrode. Some preferred catalysts are the chloride salts having the formula [Co(NH₃)₅Cl] Y_y, and especially [Co(NH₃)₅Cl]Cl2. More preferred are the present invention compositions which utilize cobalt

(III) bleach catalysts having the formula:

[Co(NH₃)_n(M)_m(B)_b] T_y wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to the cobalt by one site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n = 6, and when b=l, then m=0 and n=4; and T is one or more appropriately selected counteranions present in a number y, where y is an integer to obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when T is a -1 charged anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M"¹ s"¹ (25°C). As fully disclosed in U.S. Patent application 5,559,261 and copending patent applications U.S. Serial Nos. 08/491,185 (P&G & Case 5726), 08/491,462 (P&G Case 5727) and 08/491/,238 (P&G Case 5728) all filed on June 16, 1995, incorporated herein by reference.

As a practical matter, and not by way of limitation, the cleaning compositions and cleaning 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 dishwashing process, typical automatic dishwashing 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 by weight of the cleaning compositions. Conventional Bleach Activators

Compositions useful in the method of the present invention may also contain, additional bleach activators, in the form of conventional bleach activators. "Conventional bleach activators" herein are any bleach activators which do not respect the above-identified provisions in defining the activators herein. Levels of bleach activators herein may vary widely, e.g., from about 0.1% to about 90%, by weight of the composition, although lower levels, e.g., from about 0.1% to about 30%), or from about 0.1%) to about 20% by weight of the composition are more typically used. If an additional bleach activator is used it must be compatible with the rubber components in a domestic bleaching process. That is, the conventional additive must cause minimal, preferably no damage to the rubber components in a domestic bleaching process. Preferred hydrophilic bleach activators include N,N,N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives. TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach activators. Depending on the application, acetyl triethyl citrate, a liquid, also has some utility, as does phenyl benzoate.

Preferred hydrophobic bleach activators include substituted amide types described in detail hereinafter, such as activators related to NAPAA, and activators related to certain imidoperacid bleaches, for example as described in U.S. Patent 5,061,807, issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany.

Other suitable bleach activators include sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium- 1-methy 1-2 -benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl ammonium toluyloxy-benzene sulfonate; or sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).

Bleach activators may be used in any amount, typically up to 20%, preferably from 0.1-10%) by weight, of the composition, though higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or forms intended for appliance automated dosing. Highly preferred bleach activators useful herein are amide-substituted and have either of the formulae: O O O O

II II II II

R1-C— N— R2-C— L,

I R1— N I — C— R2-C— L

R5 R5 or mixtures thereof, wherein R is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms including both hydrophilic types (short R*) and hydrophobic types (R is especially from 6, preferably about 8, to about 12), R is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, R is H, or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is a leaving group which is herein before defined.

Preferred bleach activators also include those of the above general formula wherein L is selected from the group consisting of:

3 - + - + wherein R is as defined above and Y is -SO3 M or -CO2 M wherein M is as defined above.

Preferred examples of bleach activators of the above formulae include:

(6-octanamidocaproyl)oxybenzenesulfonate,

(6-nonanamidocaproyl)oxybenzenesulfonate,

(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof.

Other useful activators, disclosed in U.S. 4,966,723, are benzoxazin-type, such as a CβH4 ring to which is fused in the 1,2-positions a moiety ~

C(O)OC(R1)=N-. A highly preferred activator of the benzoxazin-type is:

Acyl lactam activators are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639) of the formulae:

wherein R^ is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons. See also U.S. 4,545,784 which discloses acyl caprolactams, including benzoyl caprolactam adsorbed into sodium perborate. Nonlimiting examples of additional activators useful herein are to be found in U.S. 4,915,854, U.S. 4,412,934 and 4,634,551.

Additional activators useful herein include those of U.S. 5,545,349. Examples include esters of an organic acid and ethylene glycol, diethylene glycol or glycerin, or the acid imide of an organic acid and ethylenediamine; wherein the organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p- methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2-butoxypropionic acid, p-butoxybenzoic acid, 2- methoxy ethoxyacetic acid,2-methoxy-l -methylethoxyacetic acid, 2-methoxy-2- methylethoxyacetic acid, 2-ethoxyethoxyacetic acid, 2-(2-ethoxyethoxy)propionic acid, p-(2-ethoxyethoxy)benzoic acid, 2-ethoxy-l-methylethoxyacetic acid, 2- ethoxy-2-methylethoxyacetic acid, 2-propoxy ethoxyacetic acid, 2-propoxy-l- methylethoxyaceticacid, 2-propoxy-2-methylethoxyacetic acid, 2- butoxy ethoxyacetic acid ,2-butoxy-l -methylethoxyacetic acid, 2-butoxy-2- methylethoxyacetic acid, 2-(2-methoxyethoxy)ethoxyacetic acid, 2-(2-methoxy-l- methylethoxy)ethoxyacetic acid, 2-(2-methoxy-2-methylethoxy)ethoxyacetic acid and 2-(2-ethoxyethoxy)ethoxyacetic acid.

Useful herein as oxygen bleaches are the inorganic peroxides such as Na2θ2, superoxides such as KO2, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacids and their salts such as the peroxosulfuric acid salts, especially the potassium salts of peroxodisulfuric acid and, more preferably, of peroxomonosulfuric acid including the commercial triple-salt form sold as OXONE by DuPont and also any equivalent commercially available forms such as CUROX from Akzo or CAROAT from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives rather than as primary oxygen bleach.

Mixed oxygen bleach systems are generally useful, as are mixtures of any oxygen bleaches with the known bleach activators, organic catalysts, enzymatic catalysts and mixtures thereof; moreover such mixtures may further include brighteners, photobleaches and dye transfer inhibitors of types well-known in the art. Other useful peracids and bleach activators herein are in the family of imidoperacids and imido bleach activators. These include phthaloylimidoperoxycaproic acid and related arylimido-substituted and acyloxynitrogen derivatives. For listings of such compounds, preparations and their incorporation into laundry compositions including both granules and liquids, See U.S. 5,487,818; U.S. 5,470,988, U.S. 5,466,825; U.S. 5,419,846; U.S. 5,415,796; U.S. 5,391,324; U.S. 5,328,634; U.S. 5,310,934; U.S. 5,279,757; U.S. 5,246,620; U.S. 5,245,075; U.S. 5,294,362; U.S. 5,423,998; U.S. 5,208,340; U.S. 5,132,431 and U.S. 5,087385.

Additional bleach activators are those described in U.S. Patent 5,130,045, Mitchell et al, and 4,412,934, Chung et al, and copending patent applications U. S. Serial Nos. 08/064,624, 08/064,623, 08/064,621, 08/064,562, 08/064,564, 08/082,270 and copending application to M. Burns, A. D. Willey, R. T. Hartshorn, C. K. Ghosh, entitled "Bleaching Compounds Comprising Peroxyacid Activators Used With Enzymes" and having U.S. Serial No. 08/133,691 (P&G Case 4890R), all of which are incorporated herein by reference. Quaternary substituted bleach activators may also be included. The present detergent 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 copending U.S. Patent Nos. 5,460,747, 5,584,888 and 5,578,136, incorporated herein by reference. Useful diperoxyacids include, for example, 1,12-diperoxydodecanedioic acid (DPDA); 1 ,9-diperoxyazelaic acid; diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid; 2-decyldiperoxybutane-l,4-dioic acid; and 4,4'- sulphonylbisperoxybenzoic acid. Owing to structures in which two relatively hydrophilic groups are disposed at the ends of the molecule, diperoxyacids have sometimes been classified separately from the hydrophilic and hydrophobic monoperacids, for example as "hydrotropic". Some of the diperacids are hydrophobic in a quite literal sense, especially when they have a long-chain moiety separating the peroxyacid moieties.

It is stressed that if any bleach activators are used then they are limited to ones which cause minimal, preferably no damage to the rubber components in a domestic bleaching process. Enzymatic sources of hydrogen peroxide

On a different track from the oxygen bleaching agents illustrated hereinabove, another suitable hydrogen peroxide generating system is a combination of a Cl -C4 alkanol oxidase and a Cl -C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are disclosed in WO 94/03003. Other enzymatic materials related to bleaching, such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalases and their enhancers or, more commonly, inhibitors, may be used as optional ingredients in the instant compositions.

Oxygen transfer agents and precursors Also useful herein are any of the known organic bleach catalysts, oxygen transfer agents or precursors therefor. These include the compounds themselves and/or their precursors, for example any suitable ketone for production of dioxiranes and/or any of the hetero-atom containing analogs of dioxirane precursors or dioxiranes, such as sulfonimines R1 see EP 446 982 A, published 1991 and sulfonyloxaziridines, for example:

O

1 2 / \ 3

R R C— NSO₂R see EP 446,981 A, published 1991. Preferred examples of such materials include hydrophilic or hydrophobic ketones, used especially in conjunction with monoperoxysulfates to produce dioxiranes in situ, and/or the imines described in U.S. 5,576,282 and references described therein. Oxygen bleaches preferably used in conjunction with such oxygen transfer agents or precursors include percarboxylic acids and salts, percarbonic acids and salts, peroxymonosulfuric acid and salts, and mixtures thereof. See also U.S. 5,360,568; U.S. 5,360,569; and U.S. 5,370,826. In a highly preferred embodiment, the invention relates to a detergent composition which incorporates a transition-metal bleach catalyst in accordance with the invention, and organic bleach catalyst such as one named hereinabove, a primary oxidant such as a hydrogen peroxide source, a hydrophilic bleach activator, and at least one additional detergent, hard-surface cleaner or automatic dishwashing adjunct. Preferred among such compositions are those which further include a precursor for a hydrophobic oxygen bleach such. Detersive Surfactant

The compositions used in the present invention may also additionally include a detersive surfactant. The detersive surfactant may comprise from about 0.1%, to about 99.9%), by weight of the composition depending upon the particular surfactants used and the effects desired. More typical levels comprise from about 1%) to about 80%), even more preferably from about 5%> to about 60%, by weight of the composition. Examples of suitable surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company, in U.S. 3,929,678, Dec. 30, 1975 Laughlin, et al, and U.S. 4,259,217, March 31, 1981, Murphy; in the series "Surfactant Science", Marcel Dekker, Inc., New York and Basel; in "Handbook of Surfactants", M.R. Porter, Chapman and Hall, 2nd Ed., 1994; in "Surfactants in Consumer Products", Ed. J. Falbe, Springer-Verlag, 1987 and "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) all of which are incorporated hereinbefore by reference. The detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also be used. Preferred detersive surfactants comprise anionic surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants. Methods for use in conventional front loading washing machines and automatic dishwashing compositions typically employ low sudsing detersive surfactants, such as mixed ethyleneoxy/propyleneoxy nonionics.

Those detersive surfactants which can act as a pH-reducing ionic nonsoap detersive surfactant include anionic surfactants in at least partially acidic form, semipolar surfactants, zwitterionic surfactants and mixtures of all three. Nonlimiting examples of pH reducing surfactants include the conventional Ci i .Cj alkylbenzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the Ci Q-Cjg secondary (2,3) alkyl sulfates of the formula CH₃(CH2)χ(CHOSO₃-M⁺)CH3 and CH₃(CH2)_y(CHOSO₃-M⁺) CH₂CH₃ where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Ci ø-Ci g alkyl alkoxy sulfates ("AE_XS"; especially EO 1-7 ethoxy sulfates), Ci _Q-Ci g alkyl alkoxy carboxylates (especially the EO 1-5 ethoxy carboxylates), and C12-C1 g alpha-sulfonated fatty acid esters.

Nonlimiting examples of surfactants useful herein include such as the conventional CiQ-Ci alkyl polyglycosides and their corresponding sulfated polyglycosides, Ci2-Cι g alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Ci 2-Cι g betaines and sulfobetaines ("sultaines"), Ci ø- Cjg amine oxides, and the like. Another possible surfactant are the so-called Dianionics. These are surfactants which have at least two anionic groups present on the surfactant molecule. Some suitable dianionic surfactants are further described in copending U.S. Serial No. 60/020,503 (Docket No. 6160P), 60/020,772 (Docket No. 6161P), 60/020,928 (Docket No. 6158P), 60/020,832 (Docket No. 6159P) and 60/020,773 (Docket No. 6162P) all filed on June 28, 1996, and 60/023,539 (Docket No. 6192P), 60/023493 (Docket No. 6194P), 60/023,540 (Docket No. 6193P) and 60/023,527 (Docket No. 6195P) filed on August 8th, 1996, the disclosures of which are incorporated herein by reference. Other conventional useful surfactants are listed in standard texts. Additionally, the surfactant may be a branched alkyl sulfate, branched alkyl alkoxylate, branched alkyl alkoxylate sulfate or mid chain branched alkyl aryl sulfonate. These Surfactants are further described in copending U.S. Patent applications No. 60/053,319 Attorney docket No 6766P filed on July 21st, 1997, No. 60/053,318, Attorney docket No 6767P filed on July 21st, 1997, No. 60/053,321, Attorney docket No 6768P filed on July 21st, 1997, No. 60/053,209, Attorney docket No 6769P filed on July 21st, 1997, No. 60/053,328, Attorney docket No 6770P filed on July 21st, 1997, No. 60/053,186, Attorney docket No 6771P filed on July 21st, 1997, No. 60/061,971, Attorney docket No 688 IP October 14, 1997, No. 60/061,975, Attorney docket No 6882P October 14, 1997, No. 60/062,086, Attorney docket No 6883P October 14, 1997, No. 60/061,916, Attorney docket No 6884P October 14, 1997, No. 60/061,970, Attorney docket No 6885P October 14, 1997, No. 60/062,407, Attorney docket No 6886P October 14, 1997,. Other suitable mid- chain branched surfactants can be found in U.S. Patent applications Serial Nos. 60/032,035 (Docket No. 640 IP), 60/031,845 (Docket No. 6402P), 60/031,916 (Docket No. 6403P), 60/031,917 (Docket No. 6404P), 60/031,761 (Docket No. 6405P), 60/031,762 (Docket No. 6406P) and 60/031,844 (Docket No. 6409P). Mixtures of these branched surfactants with conventional linear surfactants are also suitable for use in the present compositions. One class of nonionic surfactant particularly useful in detergent compositions used in the methods of the present invention is condensates of ethylene oxide with a hydrophobic moiety. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature. The length of the poly oxy ethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol, the C12-C15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, and mixtures thereof.

Another suitable class of nonionic surfactants comprises sugar derived surfactants such as the polyhydroxy fatty acid amides of the formula:

R²C(O)N(Rl)Z wherein: R is H, Ci -Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C -C alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R² is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9- C17 alkyl or alkenyl, most preferably straight chain C11-C19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose com syrup, high fructose com sy p, and high maltose com sy p can be utilized as well as the individual sugars listed above. These com syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH -(CHOH)_n-CH₂OH, -CH(CH2OH)- (CHOH)_n.₁-CH OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH₂OH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH₂-(CHOH)₄-CH₂OH.

Ri can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2 -hydroxy ethyl, or N-2-hydroxy propyl. For highest sudsing, Ri is preferably methyl or hydroxyalkyl. If lower sudsing is desired, Ri is preferably C2- Cg alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2- ethyl hexyl.

R2-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Cationic surfactants suitable for use in the methods of the present invention include those having a long-chain hydrocarbyl group. Examples of such cationic co- surfactants include the ammonium co-surfactants such as alkyldimethylammonium halogenides, and those co-surfactants having the formula: [R2(OR³)_y][R⁴(OR3)_y]₂R⁵N+X- wherein R^ is an alkyl or alkyl benzyl group having from 8 to 18 carbon atoms in the alkyl chain, each R? is selected from the group consisting of -CH2CH2-, - CH₂CH(CH₃)-, -CH CH(CH₂OH)-, -CH₂CH CH2-, and mixtures thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1 -C4 hydroxyalkyl, benzyl ring stmctures formed by joining the two R⁴ groups, -CH2CHOH- CHOHCOR6CHOHCH2OH wherein R^ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R^ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R^ plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

Examples of other suitable cationic surfactants are described in following documents, all of which are incorporated by reference herein in their entirety: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers, (North American edition 1997); Schwartz, et al., Surface Active Agents, Their Chemistry and Technology, New York: Interscience Publishers, 1949; U.S. Patent 3,155,591; U. S. Patent 3,929,678; U. S. Patent 3,959,461 U. S. Patent 4,387,090 and U.S. Patent 4,228,044. Examples of suitable cationic surfactants are those corresponding to the general formula:

wherein Ri , R2, R3, and R4 are independently selected from an aliphatic group of from 1 to about 22 carbon atoms or an aromatic, alkoxy, polyoxyalkylene, alkylamido, hydroxyalkyl, aryl or alkylaryl group having up to about 22 carbon atoms; and X is a salt-forming anion such as those selected from halogen, (e.g. chloride, bromide), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, and alkylsulfate radicals. The aliphatic groups can contain, in addition to carbon and hydrogen atoms, ether linkages, and other groups such as amino groups. The longer chain aliphatic groups, e.g., those of about 12 carbons, or higher, can be saturated or unsaturated. Preferred is when R\, R2, R3, and R4 are independently selected from Cl to about C22 alkyl. Especially preferred are cationic materials containing two long alkyl chains and two short alkyl chains or those containing one long alkyl chain and three short alkyl chains. The long alkyl chains in the compounds described in the previous sentence have from about 12 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms, and the short alkyl chains in the compounds described in the previous sentence have from 1 to about 3 carbon atoms, preferably from 1 to about 2 carbon atoms.

Suitable levels of cationic detersive surfactant herein are from about 0.1% to about 20%), preferably from about 1% to about 15%, although much higher levels, e.g., up to about 30% or more, may be useful especially in nonionic : cationic (i.e., limited or anionic-free) formulations.

Amphoteric or zwitterionic detersive surfactants when present are usually useful at levels in the range from about 0.1% to about 20% by weight of the detergent composition. Often levels will be limited to about 5% or less, especially when the amphoteric is costly.

Suitable amphoteric surfactants include the amine oxides corresponding to the formula: R R R" N→O wherein R is a primary alkyl group containing 6-24 carbons, preferably 10-18 carbons, and wherein R' and R" are, each, independently, an alkyl group containing 1 to 6 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Builders

Detergent builders can optionally be included in the compositions used herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in automatic dishwashing and fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. High performance compositions typically comprise from about 10% to about 80%, more typically from about 15% to about 50%) by weight, of the detergent builder. Lower or higher levels of builder, however, are not excluded.

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, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. See U.S. Pat. 4,605,509 for examples of preferred aluminosilicates.

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6® is a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 is the δ-Na2Siθ5 morphology form of layered silicate and can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi_xθ2χ+ι yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the α-, β- and γ- forms. 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. Silicates useful in automatic dishwashing (ADD) applications include granular hydrous 2-ratio silicates such as BRITESIL® H20 from PQ Corp., and the commonly sourced BRITESIL® H24 though liquid grades of various silicates can be used when the ADD composition has liquid form. Within safe limits, sodium metasilicate or sodium hydroxide alone or in combination with other silicates may be used in an ADD context to boost wash pH to a desired level.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Various grades and types of sodium carbonate and sodium sesquicarbonate may be used, certain of which are particularly useful as carriers for other ingredients, especially detersive surfactants.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: [M_z(zAlO2)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.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2[(Alθ2)i2(Siθ2)i2]"^χH2θ 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. As with other builders such as carbonates, it may be desirable to use zeolites in any physical or morphological form adapted to promote surfactant carrier function, and appropriate particle sizes may be freely selected by the formulator.

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

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

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5- trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty laundry detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used 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 of the present invention are the

3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-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.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also U.S. Patent 3,723,322. Fatty acids, e.g., Ci 2-Cι 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. In situations where phosphorus-based builders can be used, and especially in the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used. However, in general, phosphorous-based builders are not desired. Chelating Agents

The compositions used herein may also optionally contain one or more heavy metal chelating agents, such as diethylenetriaminepentaacetic acid (DTP A). More generally, chelating agents suitable for use herein can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove heavy metal ions from washing solutions by formation of soluble chelates; other benefits include inorganic film or scale prevention. Other suitable chelating agents for use herein are the commercial DEQUEST® series, and chelants from Monsanto, DuPont, and Nalco, Inc.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphoms are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

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

A highly preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially (but not limited to) the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The trisodium salt is preferred though other forms, such as magnesium salts, may also be useful.

If utilized, especially in ADD compositions, these chelating agents or transition-metal-selective sequestrants will preferably comprise from about 0.001% to about 10%, more preferably from about 0.05% to about 1% by weight of the bleaching compositions herein. Dispersant Polymers

The compositions used in the methods of the present invention may also optionally contain from about 0.1% to about 20%, more preferably from about 0.5% to about 10%) by weight of the composition of a dispersant polymer. Dispersant polymers are compounds which act as soil suspending agents in the aqueous wash liquor. That is, they act to suspend the soils in solution and prevent the soils from re-depositing on the surfaces of fabrics or dishes. This allows soils to be removed with the wash liquor. Dispersant polymers are well-known and conventional and are available from BASF Corp. and Rohm & Haas. Typical examples include polyethoxylated amines and acrylic acid/maleic acid copolymers. Soil Release Agents

The compositions according to the present invention may optionally comprise one or more soil release agents. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the laundry cycle and , thus, serve as an anchor for the hydrophilic segments. This can enable stains occuring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

If utilized, soil release agents will generally comprise from about 0.01% to about 10%) preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3% by weight, of the composition.

The following, all included herein by reference, describe soil release polymers suitable for us in the present invention. U.S. 5,691,298 Gosselink et al., issued November 25, 1997; U.S. 5,599,782 Pan et al., issued February 4, 1997; U.S. 5,415,807 Gosselink et al., issued May 16, 1995; U.S. 5,182,043 Morrall et al., issued January 26, 1993; U.S. 4,956,447 Gosselink et al, issued September 11, 1990; U.S. 4,976,879 Maldonado et al. issued December 11, 1990; U.S. 4,968,451 Scheibel et al., issued November 6, 1990; U.S. 4,925,577 Borcher, Sr. et al., issued May 15, 1990; U.S. 4,861,512 Gosselink, issued August 29, 1989; U.S. 4,877,896 Maldonado et al., issued October 31, 1989; U.S. 4,771,730 Gosselink et al., issued October 27, 1987; U.S. 711,730 Gosselink et al, issued December 8, 1987; U.S. 4,721,580 Gosselink issued January 26, 1988; U.S. 4,000,093 Nicol et al., issued December 28, 1976; U.S. 3,959,230 Hayes, issued May 25, 1976; U.S. 3,893,929 Basadur, issued July 8, 1975; and European Patent Application 0 219 048, published April 22, 1987 by Kud et al. Further suitable soil release agents are described in U.S. 4,201,824 Voilland et al.; U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S. 4,579,681 Ruppert et al.; U.S. 4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone- Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N.V., 1974; all incorporated herein by reference. Detersive Enzymes

The compositions of the present invention may also include the presence of at least one detersive enzyme. "Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a composition. Suitable optional enzymes include cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more bleach compatible, have a remaining degree of bleach deactivation susceptibility.

In general, as noted, preferred compositions herein comprise one or more detersive enzymes. If only one enzyme is used, it is preferably an amyolytic enzyme when the composition is for automatic dishwashing use. Highly preferred for automatic dishwashing is a mixture of proteolytic enzymes and amyloytic enzymes. More generally, the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders, etc. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Enzymes are normally incorporated in the instant detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning- effective amount" refers to any amount capable of producing a cleaning, stain removal or soil removal effect on substrates such as fabrics, dishware and the like. Since enzymes are catalytic materials, such amounts may be very small. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 6%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For automatic dishwashing purposes, it may be desirable to increase the active enzyme content of the commercial preparations, in order to minimize the total amount of non-catalytically active materials delivered and thereby improve spotting/filming results.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S as ESPERASE®. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASE® and SAVINASE® by Novo Industries A/S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985). An especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO 95/10615 published April 20, 1995 by Genencor International. Other preferred protease enzymes include protease enzymes which are a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived by replacement of a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond to position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +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 positions correspond to naturally-occurring subtilisin from Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin). Preferred enzymes according include those having position changes +210, +76, +103, +104, +156, and +166.

Useful proteases are also described in PCT publications: WO 95/30010 published November 9, 1995 by The Procter & Gamble Company; WO 95/30011 published November 9, 1995 by The Procter & Gamble Company; WO 95/29979 published November 9, 1995 by The Procter & Gamble Company.

Amylases suitable herein include, for example, α-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE®, International Bio- Synthetics, Inc. and TERMAMYL®, Novo Industries.

Preferred amylases herein have the commonalty of being derived using site- directed mutagenesis from one or more of the Baccillus amylases, especially the Bacillus alpha-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. As noted, "oxidative stability-enhanced" amylases are preferred for use herein despite the fact that the invention makes them "optional but preferred" materials rather than essential. Such amylases are non-limitingly illustrated by the following: (a) An amylase according to the hereinbefore incorporated WO/94/02597,

Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.stearothermophilus;

(b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®;

(c) Also preferred herein are amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S and are those referred to by the supplier under the tradename DURMAMYL®; (d) Particularly preferred are amylase variants as disclosed in WO95/26397 and in the co-pending application to Novo Nordisk PCT/DK96/00056 and 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 and is obtained from an alkalophilic Bacillus species (such as the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935) comprising the following amino acid sequence in the N-terminal: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr- Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp

Cellulases usable in, but not preferred, for the present invention include both bacterial or fungal cellulases. Typically, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME® (Novo) is especially useful.

Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. Another preferred lipase enzyme is the D96L variant of the native Humicola lanuginosa lipase, as described in WO 92/05249 and Research Disclosure No. 35944, March 10, 1994, both published by Novo. In general, lipolytic enzymes are less preferred than amylases and/or proteases for automatic dishwashing embodiments of the present invention.

Peroxidase enzymes can be used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are typically used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S. The present invention encompasses peroxidase- free automatic dishwashing composition embodiments.

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570. Brightener

Any optical brighteners or other brightening or whitening agents known in the art can be present at levels typically from about 0.05% to about 1.2%, by weight, in the compositions used herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-stryl-phenyl)-2H-napthol[l,2-d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(- venzimidazol-2-yl)ethylene; 1 ,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2- yl)thiophene; 2-stryl-napth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2- dltriazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners are preferred herein. Other additives

Usual ingredients can include one or more materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the composition. Usual detersive adjuncts of detergent compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which can also be used in the compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to about 20% of the detergent ingredients, preferably from about 0.5% to about 10%>), include other active ingredients such as enzyme stabilizers, color speckles, anti-tarnish and/or anti-corrosion agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizing agents, perfumes, dyes, solubilizing agents, clay soil removal/anti-redeposition agents, carriers, processing aids, pigments, solvents for liquid formulations, fabric softeners, static control agents, solid fillers for bar compositions, etc. Dye transfer inhibiting agents, including polyamine N-oxides such as polyvinylpyridine N-oxide can be used. Dye-transfer-inhibiting agents are further illustrated by polyvinylpyrrolidone and copolymers of N-vinyl imidazole and N-vinyl pyrrolidone. If high sudsing is desired, suds boosters such as the CjQ-Cig alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%>-5%> of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. Form of composition

The compositions of the present invention can be in any of the conventional forms. This includes, but is not limited to, solids, bars, powders, granules, both high bulk density 550g/l or higher and the so-called "fluffy" granules with a bulk density of 400 g/1 or less, tablets, liquids, both aqueous and non-aqueous, liquid-gels and flakes.

Liquid Compositions The present invention can use a liquid including the aforementioned ingredients. Liquid compositions, including gels, typically contain some water and other fluids as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used. The compositions may contain from 5% to 90%>, typically 10% to 50%> of such carriers. Methods using liquid compositions according to the present invention are formulated acidic to deliver an in-use alkaline pH. Formulation pH is generally from about 2 to about 5 and preferably from about 2.5 to about 4.5. In-use pH is generally from about 7 to about 9.5, preferably from about 7.5 to about 8.5. The use of lower formulation pH provides for more stability of the cyclic imido activator in solution. Furthermore, when formulating liquid compositions, the source of hydrogen peroxide, if any, is preferably hydrogen peroxide itself. Coating

Various detersive ingredients employed in the compositions used in the present invention can optionally be further stabilized by absorbing the ingredients onto a porous hydrophobic substrate, then coating the substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being adsorbed into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT®D10, Degussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13.15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. Granular Compositions

Various means and equipment are available to prepare high density (i.e., greater than about 550, preferably greater than about 650, grams/liter or "g/1"), high solubility, free-flowing, granular detergent compositions according to the present invention. Current commercial practice in the field employs spray-drying towers to manufacture granular laundry detergents which often have a density less than about 500 g/1. In this procedure, an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of about 175°C to about 225°C. However, if spray drying is used as part of the overall process herein, additional process steps as described hereinafter must be used to obtain the level of density (i.e., > 650 g/1) required by modem compact, low dosage detergent products.

For example, spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers. A suitable high speed mixer/densifier for this process is a device marketed under the tradename "Lδdige CB 30" or "Lδdige CB 30 Recycler" which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon. In use, the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued September 22, 1992. The preferred residence time in the high speed mixer/densifier is from about 1 to 60 seconds. Other such apparatus includes the devices marketed under the tradename "Shugi Granulator" and under the tradename "Drais K-TTP 80).

Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower intraparticle porosity. Equipment such as that marketed under the tradename "Lόdige KM" (Series 300 or 600) or "Lδdige Ploughshare" mixer/densifiers are suitable for this process step. Such equipment is typically operated at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer/densifier is from about 0.1 to 12 minutes conveniently measured by dividing the steady state mixer/densifier weight by the throughput (e.g., Kg/hr). Other useful equipment includes the device which is available under the tradename "Drais K-T 160". This process step which employs a moderate speed mixer/densifier (e.g. Lόdige KM) can be used by itself or sequentially with the aforementioned high speed mixer/densifier (e.g. Lόdige CB) to achieve the desired density. Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942. While it may be more suitable to use the high speed mixer/densifier followed by the low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention. By way of example, see the processes in Appel et al, U.S. Patent 5,133,924, issued July 28, 1992 (granules are brought into a deformable state prior to densification); Delwel et al, U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray- dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). In those situations in which particularly heat sensitive or highly volatile detergent ingredients are to be incorporated into the final detergent composition, processes which do not include spray drying towers are preferred. The formulator can eliminate the spray-drying step by feeding, in either a continuous or batch mode, starting detergent ingredients directly into mixing/densifying equipment that is commercially available. One particularly preferred embodiment involves charging a surfactant paste and an anhydrous builder material into a high speed mixer/densifier (e.g. Lόdige CB) followed by a moderate speed mixer/densifier (e.g. Lδdige KM) to form high density detergent agglomerates. See Capeci et al, U.S. Patent 5,366,652, issued November 22, 1994 and Capeci et al, U.S. Patent 5,486,303, issued January 23, 1996. Optionally, the liquid/solids ratio of the starting detergent ingredients in such a process can be selected to obtain high density agglomerates that are more free flowing and crisp.

Optionally, the process may include one or more recycle streams of undersized particles produced by the process which are fed back to the mixer/densifiers for further agglomeration or build-up. The oversized particles produced by this process can be sent to grinding apparatus and then fed back to the mixing/densifying equipment. These additional recycle process steps facilitate build-up agglomeration of the starting detergent ingredients resulting in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550 g/1). See Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996. Other suitable processes which do not call for the use of spray-drying towers are described by Bollier et al, U.S. Patent 4,828,721, issued May 9, 1989; Beerse et al, U.S. Patent 5,108,646, issued April 28, 1992; and, Jolicoeur, U.S. Patent 5,178,798, issued January 12, 1993.

In yet another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the various ingredients of the finished composition are combined in an aqueous slurry (typically 80% solids content) and sprayed into a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this process can optionally include the step of mixing the slurry using the aforementioned Lόdige CB mixer/densifier or a "Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving beds of the type available under the tradename "Escher Wyss" can be used in such processes.

Another suitable process which can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lόdige KM) for further agglomeration resulting in the finished high density detergent composition. See Appel et al, U.S. Patent 5,164,108, issued November 17, 1992.

Optionally, high density detergent compositions according to the invention can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein. Additional adjunct ingredients such as enzymes, perfumes, brighteners and the like can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.

Another process for the manufacture of granules for use in the novel process comprises the steps of:

(i) preparing a mix of solids, and optionally liquids, comprising the bleach activator; (ii) extmding the mix through a die under pressure to form an extrudate;

(iii) breaking the extrudate to form a spheronised extrudate; and (iv) optionally coating the particles to improve friability and flow characteristics.

The mixing step (i) is carried out using any conventional powder/liquid mixer, e.g. a Loedige KM mixer. The extmding step (ii) can be achieved using any conventional extmder which can be axial, radial or more preferably dome-type, e.g. Fuji Paudal Model DGL-1, most preferably having a die with O.lmm orifices and extmded at pressures of about 20 bar. Step (iii) is preferably carried out using a rotating disc spheroniser such as a Fuji Paudal QJ-1000 where the extmdates are broken down into short lengths and formed into substantially spherical particles.

Additionally, the extmdates may then be dried in a vibrating fluid bed drier, e.g. Niro, to result in crisp, free-flowing particles with a particle size range of from 0.25mm to 20mm and a Heubach dust measurement of less than 1 OOmg/g.

The optional coating step (iv) could involve materials such as film forming polymers or preferably a liquid fixative, e.g. nonionic surfactant and an inert powder such as Zeolite A. See WO9800504, published January 8, 1998 and WO 97277280, published July 31, 1997. The present invention will now be described by reference to the following examples. Of course, one of ordinary skill in the art will recognize that the present invention is not limited to the specific examples herein described or the ingredients and steps contained therein, but rather, may be practiced according to the broader aspects of the disclosure. EXAMPLE 8

Bleaching compositions having the form of granular laundry detergents are exemplified by the following formulations.

*Bleach activator according to any of Examples 1-7

EXAMPLE 9 This Example illustrates bleaching compositions, more particularly, liquid bleach additive compositions in accordance with the invention.

1 Alkyl ethoxylate available from The Shell Oil Company.

2 Commercially available from Monsanto Co.

3 Bleach Activator according to any of Examples 1-7.

EXAMPLE 10 This Example illustrates cleaning compositions having bleach additive form, more particularly, liquid bleach additive compositions without a hydrogen peroxide source in accordance with the invention.

1 Alkyl ethoxylate available from The Shell Oil Company.

2 Commercially available from Monsanto Co.

3 Bleach Activator according to any of Examples 1-7.

The compositions are used as bleach boosting additive (to be used in ADDITION to a bleach detergent such as TIDE® WITH BLEACH). The additive is used at 1000 ppm,

EXAMPLE 11 Bleaching compositions having the form of granular laundry detergents are exemplified by the following formulations.

*Bleach activator according to any of Examples 1-7

Any of the above compositions is used to launder fabrics under mildly alkaline conditions (pH 7 - 8). The pH can be adjusted by altering the proportion of acid to Na- salt form of alkylbenzenesulfonate.

EXAMPLE 12 A granular automatic dishwashing detergent composition comprises the following.

Note 1 :Bleach Activator according to any of Examples 1-7.

Note 2: These hydrogen peroxide sources are expressed on a weight % available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.

Note 3 transition Metal Bleach Catalyst: Pentamaineacetatocobalt (III) nitrate; may be replaced MnTACN.

EXAMPLE 13 A granular automatic dishwashing detergent composition comprising the following.

Note LBleach Activator according to any of Examples 1 -7.

Note 2: These hydrogen peroxide sources are expressed on a weight % available oxygen basis. To convert to a basis of percentage of the total composition, divide by about 0.15.

Note 3 transition Metal Bleach Catalyst: Pentamaineacetatocobalt (III) nitrate; may be replaced MnTACN.

Note 4: Sodium tripolyphosphate.

Note 5: The amylase is selected from: Termamyl®, Fungamyl®; Duramyl®; BAN®, and the amylases as described in WO95/26397 and in co-pending application by

Novo Nordisk PCT/DK/96/00056.

Note 6: The protease is selected from: Savinase®; Maxatase®; Maxacal®;

Maxapem 15®; subtilisin BPN and BPN'; Protease B; Protease A; Protease C,

Protease D; Primase®; Durazym®; Opticlean®;and Optimase®; and Alcalase ®.

Claims

WHAT IS CLAIMED IS:

1. A method of reducing or preventing degradation of mbber, in a domestic bleaching process, comprising the steps of contacting a substrate comprising mbber with a detergent composition including a bleach additive selected from the group consisting of:

(a)

(b)

(c)

(d)

(e)

; and (f) mixtures thereof; wherein, any of said moieties, A, E and X comprise substituted or unsubstituted hydrocarbyl groups, M is selected from hydrogen and compatible cations having a charge q; and y and z are integers such that said compound is electrically neutral; and L is a leaving group or OH.

2. A method for cleaning fabrics in an automatic washing machine having parts made of mbber which is susceptible to oxidative degradation, said method comprising agitating said fabrics in said machine in an aqueous liquor comprising a bleach additive selected from the group consisting of: (a)

(b)

(c)

(d)

(e)

and

(f) mixtures thereof; wherein, any of said moieties, A, E and X comprise substituted or unsubstituted hydrocarbyl groups, M is selected from hydrogen and compatible cations having a charge q; and y and z are integers such that said compound is electrically neutral; and L is a leaving group or OH; and such that said mbber parts of said machine are substantially undamaged by the bleaching system.

3. A method according to any preceding claim, wherein, in any of said compounds, X is selected from substituted or unsubstituted, branched or linear C\ -C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkylene; A is selected from:

Rl

wherein n denotes the number 0, 1, 2, 3 or 4; Rl is selected from the group consisting of hydrogen, chloride, bromide, iodide, substituted or unsubstituted branched or linear C1-C20 alkyl, substituted or unsubstituted branched or linear C2- C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl; R² is selected from the group consisting of hydrogen, chloride, bromide, iodide, SO3M_zq⁺, SO4M_zq⁺, COOM_zq⁺, substituted or unsubstituted branched or linear Ci -C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl; R^ and R4 are independently selected from hydrogen and Ci -Cg substituted or unsubstituted branched or linear alkyl; and each E is independently selected from the group consisting of substituted or unsubstituted, branched or linear C1 -C20 alkyl, substituted or unsubstituted, branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted, branched or linear alkylaryl.

4. A method according to any preceding claim, wherein A is selected from:

5. A method according to any preceding claim, wherein the bleach additive is selected from:

, or mixtures thereof; wherein m is an integer selected from the range 0 to 14; Rl is selected from the group consisting of hydrogen, chloride, bromide, iodide, substituted or unsubstituted branched or linear C1-C20 alkyl, substituted or unsubstituted branched or linear C2- C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl; R - is selected from the group consisting of hydrogen, chloride, bromide, iodide, SO3M_z ⁺, SO4M_z ⁺, COOM_zq⁺, substituted or unsubstituted branched or linear Ci -C20 alkyl, substituted or unsubstituted branched or linear C2-C20 alkenyl, substituted or unsubstituted aryl, and substituted or unsubstituted alkylaryl; and L is a leaving group.

6. A method according to any preceding claim, wherein said composition contains a conventional additive.

7. A method according to any preceding claim, wherein said conventional additive is selected from the group consisting of surfactants, builders, a source of hydrogen peroxide, fabric softeners, bleach catalyst, bleach activator, chelating agents, dispersant polymers, soil releases agent, enzymes, brightners and mixtures thereof.

8. A method according to any preceding claim, wherein said domestic bleaching process is performed in a front loading washing machine.

9. A method according to any preceding claim, wherein said mbber is natural mbber.

10. A method according to any preceding claim, wherein said parts are selected from the group consisting of sump hoses, door seals, motor gaskets and mixtures thereof.