WO1994010284A1

WO1994010284A1 - Granular detergents with protease enzyme and bleach

Info

Publication number: WO1994010284A1
Application number: PCT/US1993/009930
Authority: WO
Inventors: David Neil Di Giulio; Edward Eugene Getty; Chanchal Kumar Ghosh
Original assignee: The Procter & Gamble Company
Priority date: 1992-10-23
Filing date: 1993-10-18
Publication date: 1994-05-11
Also published as: DE69324261D1; MX9306634A; DE69324261T2; EP0665876A1; ATE178352T1; PL308475A1; BR9307300A; ES2131125T3; HUT71729A; HU217918B; KR950704466A; EP0665876B1; MA23011A1; DK0665876T3; CA2147658A1; JPH08502546A; AU5406394A; EG20573A; PL175424B1; CN1090599A

Abstract

Granular detergent compositions comprising certain levels of detergent surfactant, bleaching agent and protease enzyme are presented. The bleaching agent is substantially insoluble organic peroxyacid or bleach activator and peroxygen bleaching compound.

Description

GRANULAR DETERGENTS WITH PROTEASE ENZYME AND BLEACH

TECHNICAL FIELD The present invention relates to granular detergent compositions comprising certain levels of bleaching agent, protease enzyme, and detergent surfactant. The bleaching agent is substantially water-insoluble organic peroxyacid or a combination of certain bleach activators and peroxygen bleaching compound capable of yielding hydrogen peroxide.

BACKGROUND OF THE INVENTION

It has been found that certain levels of substantially water-insoluble peroxyacid bleaches, and/or bleach activators/peroxygen bleaching compounds, can be used with certain levels of protease enzyme in granular detergent compositions to obtain surprisingly effective cleaning. The combined effect of the peroxyacid, which bleaches, and the protease, which hydrolyzes protein based stains, is greater in this granular detergent composition than expected, especially in light of the fact that bleach is known to oxidize enzymes. Without meaning to be bound by theory, it is believed that at these levels, there is a synergy between the peroxyacid and the protease so that the combined cleaning effect of the two is greater than the additive effect of each one separately.

EP 0 359 087, published March 21, 1990, describes an activated oxidant system for in situ generation of peracid in aqueous media comprising protease and a specified ester substrate, along with a source of peroxygen. U.S. Patent 3,974, 082, Weyn, issued August 10, 1976, describes a bleaching composition and method utilizing a percompound, an acyl-alkyl ester, and an ester-hydrolyzing enzyme.

SUMMARY OF THE INVENTION

This invention relates to granular detergent compositions which provide especially effective surface cleaning of textiles. This invention also relates to methods for cleaning fabrics using such detergent compositions.

The granular detergent compositions of this invention comprise: a) a bleaching agent which either is from 0.5% to 20% of an organic peroxyacid or is a combination of from 0.5% to 20% of a bleach activator and a peroxygen compound capable of yielding hydrogen peroxide that can react with the activator to form an organic peroxyacid in situ in a bleaching solution formed from the composition; b) from about 0.064 to about 0.64 mg of active protease enzyme per gram of composition wherein the protease enzyme is present in an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available 02 of the peroxyacid ranging from about 1:1 to about 20:1; and c) from about 1% to about 40% by weight of the composition of a detergent surfactant which can be anionic, nonionic, ampholytic or zwitterionic surfactants or combinations thereof.

The peracid which is in the composition, or which is formed by the combination of activator and peroxygen compound, has a corresponding carboxylic acid that has a Hydrophobic-Lipophilic Balance value which ranges from about 3 to about 6.5. When the composition utilizes a combination of activator and peroxygen compound, the molar ratio of hydrogen peroxide yielded by the peroxygen compound to the activator is greater than about 1.5. Furthermore, when such an activator/peroxygen compound combination is utilized, the activator can have the formula: (I)

R - C - L;

(II) Rδ 0 0

I II II l . N - C - R2 - C - L; or

(III) 0 R5 0

II I II

Rl . c - N - R2 - C - L; wherein R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms; R- is an alkyl group containing from about 6 to about 12 carbon atoms; R² is an alkylene containing from 1 to about 6 carbon atoms; Rδ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms; and L is a leaving group, the conjugate acid of which has a pK_a in the range of from about 6 to about 13.

DETAILED DESCRIPTION OF THE INVENTION The granular detergent compositions herein (see above summary) are preferably nonphosphate granular (powder) laundry detergents which contain both bleach and enzyme for good cleaning of soiled laundry. For purposes of this invention, the term "granular" refers to detergent compositions in any suitable solid form, e.g., granules, powders, agglomerates, laundry bars, etc.

Granular laundry detergent compositions herein provide effective and efficient surface cleaning of textiles, particularly grass stains, over a wide range of laundry washing temperatures. Laundry wash solutions are preferably at temperatures between about 5*C and about 80^*C, preferably between about 10^*C and about 60^*C, for this cleaning benefit. A. Bleaching Agent

The granular detergent compositions herein contain a bleaching agent, which preferably comprises from about 0.5 to about 20 wt.% of the detergent composition. The bleaching agent is either a substantially insoluble, preferably solid, organic peroxyacid, or a bleach activator and a peroxygen bleaching compound capable of yielding hydrogen peroxide, or a combination of both.

1. Bleach Activator and Peroxygen Bleaching Compound The bleach activator has the following structure: 0

II R - C - L wherein R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pk_a in the range of from about 6 to about 13, preferably from about 7 to about 11, most preferably from about 8 to about 11.

L can be essentially any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid. Generally, for a group to be a suitable leaving group it must exert an electron attracting effect. This facilitates the nucleophilic attack by the perhydroxide anion.

The L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize. These characteristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention are known.

Preferred bleach activators are those of the general formula: R5 0 0 0 Rδ 0

I II II II I II

Rl . N - C - R2 - C - L or Rl - C - N - R2 - C - L wherein R is an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is selected from the group consisting of:

R3

Y R3

I I

0 - CH - C - CH - CH2, - 0 - C - CHR*, and - N - S - CH - R*

I II

R3 0 wherein Rδ is an alkylene, arylene, or alkarylene group containing from about 1 to about 14 carbon atoms, R3 is an alkyl chain containing from about 1 to about 8 carbon atoms, R is H or R³, and Y is H or a solubi11zing group. Y is preferably selected from the group consisting of --SO3-M+, --C00-M+, --SO4-M+, (--N+R'3)X- and 0<-N(R^,3), wherein R' is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is an anion selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions. More preferably, Y is --SO3-M+ and --C00-M+. It should be noted that bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleach solution in order to assist in their dissolution. Preferred is:

wherein R³ is as defined above and Y is --SO3-M+ or --C00-M+ wherein M is as defined above.

Especially preferred bleach activators are those wherein R¹ is a linear alkyl chain containing from about 6 to about 12 carbon atoms, R² is a linear alkylene chain containing from about 2 to about 6 carbon atoms, R⁵ is H, and L is selected from the group consisting of:

wherein R3 is as defined above, Y is --SO3-M+ or --C00-M+ and M is as defined above.

A preferred bleach activator is: 0

wherein R is H, alkyl, aryl or alkaryl. This is described in U.S. Patent 4,966,723, Hodge et al, incorporated by reference herein. Preferred bleach activators are:

0 0 0

wherein Rl is H or an alkyl group containing from about 1 to about 6 carbon atoms and R2 is an alkyl group containing from about 1 to about 6 carbon atoms and L is as defined above.

Preferred bleach activators are also those of the above general formula wherein L is as defined in the general formula, and R¹ is H or an alkyl group containing from about 1 to about 4 carbon atoms, and R² is an alkyl group containing from about 1 to about 4 carbon atoms.

Even more preferred are bleach activators of the above general formula wherein L is as defined in the general formula and Rl is a H.

A more preferred bleach activator is: 0

II

R - C - L

More preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from about 5 to about 9 and preferabiy from about 6 to about 8 carbon atoms and L is selected from the group consisting of:

R2 R2

CH - C - CH - CH2 , CHR3,

wherein R, R², R³ and Y are as defined above.

Particularly preferred bleach activators are those of the above general formula wherein R is an alkyl group containing from about 5 to about 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the carbonyl carbon is from about 6 to about 10 carbon atoms, and L is selected from the group consisting of:

Y R2 R2γ

wherein R² is an alkyl chain containing from about 1 to about 8 carbon atoms, and Y is --SO-3M+ or --C00-M+ wherein M is an alkali metal, ammonium or substituted ammonium cation.

Especially preferred bleach activators are those of the above general formula wherein R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and L is selected from the group consisting of:

wherein R2 is as defined above and Y is --SO-3M+ or --C00-M+ wherein M is as defined above.

The most preferred bleach activators have the formula: 0

wherein R is a linear alkyl chain containing from about 5 to about 9 and preferably from about 6 to about 8 carbon atoms and M is sodium or potassium.

The level of bleach activator within the compositions of the invention is preferably from about 0.5 to about 20, more preferably from about 1 to about 10, most preferably from about 2 to about 7, wt.% of the composition.

The bleaching mechanism generally, and the surface bleaching mechanism in particular, are not completely understood. However, it is generally believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form a peroxycarboxylic acid. This reaction is commonly referred to as perhydrolysis.

When the activators are used, optimum surface bleaching performance is obtained with wash solutions wherein the pH of such solution is between about 8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the perhydrolysis reaction. Such pH can be obtained with substances commonly known as buffering agents, which are optional components of the bleaching compositions herein.

Preferably, the bleach activator herein is sodium nonanoyl- oxybenzenesulfonate (NOBS) or sodium benzoyloxybenzenesulfonate (BOBS).

The molar ratio of hydrogen peroxide yielded by the peroxygen bleaching compound to the bleach activator is greater than about 1.5, preferably from about 2.0 to about 10. Preferably, the detergent compositions herein comprise from about 0.5 to about 20, most preferably from about 1 to about 10, wt.% of the peroxygen bleaching compound.

Salts of perborate and percarbonate are preferred peroxygen bleaching compounds for use herein. Sodium perborate and sodium carbonate peroxyhydrate are most preferred.

It is preferred that peroxyacids ara formed in situ in the laundry wash water by the combination of the peroxygen bleaching compound and the bleaching activator. 2. Peroxyacid

The peroxyacid herein comprises from about 0.5 to about 20, preferably from about 1 to about 10, most preferably from about 2 to about 7, wt.% of the detergent composition.

Preferred organic peroxyacids are selected from the group consisting of 4-nonylamino-4-oxoperoxybutyric acid; 6-(nonyl- amino)-6- oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid,; heptyl sulfonylperpropionic acid; decylsulphonyl perpropionic acid; and heptyl-, octyl-, nonyl-, decyl-sulphonylperbutyric acids; and mixtures thereof.

Of the organic peroxyacids, amidoperoxyacids (amide substituted peroxycarboxylic acids) are preferred. Suitable amidoperoxyacids for use herein are described in U.S. Patents 4,634,551 and 4,686,063, both Burns et al, issued January 6, 1987 and August 11, 1987, respectively, both incorporated herein by reference. Suitable amidoperoxyacids are of the formula:

Rl - NH - C - R2 - C - 00H or R1-C-NH-R2-C-00H

II II II II

0 0 0 0 wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, and R² is an alkylene group containing from 1 to about 6 carbon atoms. Preferably, Rl is an alkyl group containing from about 8 to about 10 carbon atoms, and R² is an alkylene group containing from about 2 to about 4.

Also suitable for use herein are peroxyfumarates, which are described in U.S. Patent 4,852,989, Burns et al, issued August 1, 1989, incorporated herein by reference, and sulfone peroxyacids (sulfone peroxycarboxylic acids), which are described in U.S. Patents 4,758,369, 4,824,591, and 5,004,558, all Dryoff et al, issued July 19, 1988, April 25, 1989, and April 2, 1991, respectively, all incorporated herein by reference.

Example I of U.S. Patent 4,686,063 contains one description of the synthesis of NAPSA, from column 8, line 40 to Column 9, line 5, and NAPAA, from column 9, line 15 to column 9, line 65. At the end of the amidoperoxyacid synthesis, the reaction is quenched with water, filtered, washed with water to remove some excess sulfuric acid (or other strong acid with which the peroxyacid was made), and filtered again.

The amidoperoxyacid wet cake thus obtained can be contacted with a phosphate buffer solution at a pH between about 3.5 and 6, preferably between about 4 and 5, according to U.S. Patent 4,909,953, Sadlowski et al, issued March 20, 1990, which is incorporated herein by reference.

Other agents for storage stabilization or exotherm control can be added to the amidoperoxyacid before incorporation into the final product. For example, boric acid, an exotherm control agent disclosed in U.S. Patent 4,686,063, Burns, issued August 11, 1987 and incorporated herein, can be mixed with the amidoperoxyacid (which has been washed in phosphate buffer) in about a 2:1 peracid:boric acid ratio. The phosphate buffer washed amidoperoxyacid can also be mixed with appropriate amounts of dipicolinic acid and tetrasodium pyrophosphate, a chelating stabilization system. Chelants can optionally be included in the phosphate buffer before contact with the wet cake.

The wet cake is preferably made up of particles with an average particle diameter of from about 0.1 to about 260 microns, preferably from about 10 to about 100 microns, and most preferably from about 30 to about 60 microns. Small particle size NAPAA crystals are desired herein. See U.S. Patent 5,055,218, Getty et al, issued October 8, 1991, which is incorporated herein by reference.

NAPAA filter cake herein is preferably washed twice in phosphate buffer. It has been found that two successive phosphate buffer washes lend optimal stability to NAPAA. Particulate (solid), organic peroxyacids with a theoretical AvO (available oxygen) of between about 3 and about 12, most preferably between 5 and 7, are preferred.

Most preferred for use herein is NAPAA. Another name for the nonylamide of £eroxyadipic acid ("NAPAA") is 6-(nonylamino)-6- oxoperoxycaproic acid. The chemical formula for NAPAA is: H O 0

I II II

CH3(CH2)8N C (CH2)4C00H The molecular weight of NAPAA is 287.4.

Detergent compositions and bleaching compositions containing NAPAA provide extremely effective and efficient surface bleaching of textiles. Stains and/or soils are removed from the textiles. These compositions are particularly effective at removing dingy soils from textiles.

NAPAA's polar amide or substituted amide moiety results in a peroxyacid which has a very low vapor pressure and thus possesses a low odor profile as well as excellent bleaching performance. It is believed that the polarity of the amide group results in a reduction of vapor pressure of the peroxyacid, and an increase in melting point.

NAPAA can be used directly as a bleaching agent. It has a reduced vapor pressure and a good odor profile in laundry applications.

NAPAA can be prepared by, for example, first reacting NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide. The reaction product is quenched by addition to ice water followed by filtration, washing with distilled water, and final suction filtration to recover the wet cake. Washing can be continued until the pH of the filtrate is neutral.

It is also preferred that the NAPAA pH (10% solids in water) be between about 4.2 and 4.8. Surprisingly, this pH results in more thermally stable particles.

While not wishing to be bound by theory, the present invention is based on the use of relatively hydrophobic (lipophilic) peracids (from activators or as preformed peroxyacids) which are thought to concentrate at the soil/fabric interface and enhance the performance benefits from protease enzymes. A method that can be used to characterize the selected peroxyacids (from activators or as preformed peroxyacids) which are useful in the present invention is the "H.L.B. Scale" such as that described in Davies, J.T., Proc. 2nd Internat. Conor. Surface Activity 1. 426, Butterworths, London (1957), incorporated herein by reference. Such an H.L.B. Scale (Hydrophilic-Lipophilic Balance) has been used in the study of surface-active agents (surfactants) as a means to relate the distribution of a surface-active agent between a hydrophilic (water-like) and a lipophilic (oil-like) phase. In this manner, H.L.B. values can be used as an indication of the lipophilic (hydrophobic) character of the active bleaching species in the wash (i.e., the ability of the peroxyacid to partition out of the wash liquor and concentrate at the soil/fabric interface).

Set forth hereinafter in Table A are H.L.B. values which have been calculated for selected peroxyacids (as the corresponding carboxylic acids). The equation used to calculate the H.L.B. values can be set forth as:

HLB » Sum (Hydrophilic Group Numbers) - Sum (Hydrophobic

Group Numbers) + 7.

The values for the Hydrophilic Group Numbers are [-C(0)0H &

-N(H)C(0)-*2.1] and the values for the Hydrophobic Group Numbers are [aliphatic/aromatic carbon - 0.475 & aliphatic carbon atoms between polar groups are 1/2 the value of an aliphatic carbon in a hydrocarbon chain « (0.475)/2], For reference, an H.L.B. value >7 indicates that the material is preferentially water soluble and an

H.L.B. value <7 indicates increasing surface-activity and hydrophobicity.

TABLE A

H.L.B. Values Provided by Various Peroxyacids

H.L.B. Activator/Preformed Abbrevi- Corresponding

Peroxyacid ation Peroxyacid Carboxylic Acid

Tetra Acetyl TAED CH3C(0)00H 8.6 Ethylene Diamine

PerLauric Acid PLA Q_3(CH2)ioC(0)OOH 3.9

A preferred range of H.L.B. values (as the carboxylic acid for the peroxyacids of the present invention (whether added directly or generated in situ) ranges from about 3.0 to about 6.5. A more preferred range of H.L.B. values (as the carboxylic acid) for the peroxyacids useful in the present invention (whether added directly or generated in situ) range from about 4.0 to 6.5. The most preferred range of H.L.B. values (as the carboxylic acid) for the peroxyacids of the present invention (whether added directly as generated in situ) ranges from about 4.0 to about 6.0. B. Protease Enzvmes

The detergent compositions of the present invention also comprise from about 0.064 to about 0.64, preferably from about 0.096 to about 0.32, mg of active protease enzyme per gram of composition.

Mixtures of proteolytic enzyme (protease) are also included. The proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants.

Suitable proteases include Alcalase®, Esperase^®, Savinase^® (preferred); Maxatase^®, Maxacal® (preferred), and Maxape 15^® (protein engineered Maxacal^®); and subtilisin BPN and BPN' (preferred); which are commercially available. Also suitable are modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Most preferred is what is called herein "Protease C", which is a triple variant of an alkaline serine protease from Bacillus in which tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to W0 91/06637, Published May 16, 1991, which is incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein.

Preferred proteolytic enzymes, then, are selected from the group consisting of Savinase^®, Maxacal^®, BPN', Protease A, Protease B, Protease C, and mixtures thereof. Protease B and Protease C are most preferred. Bacterial serine protease enzymes obtained from Bacillus subtilis and/or Bacillus licheniformis are preferred.

The enzymes of the present invention provide effective and efficient removal of stains and/or soils on textiles. The enzymes are particularly efficient at removing protein based stains and/or soils from textiles. While not wishing to be bound by theory, it is believed that surface active bleaches are required since the enzymes of the present invention remove stains and/or soils from the fabric surface, thereby reducing the stain and/or soils load at the fabric surface and resulting in efficient use of both bleach and enzyme.

Since the improved cleaning performance provided by the present invention is believed to result from a synergistic effect between a relatively hydrophobic peracid and protease enzymes, it is possible to express the preferred concentrations of protease enzyme and peroxyacid (whether added directly or generated in situ) as a range of ratios as well as concentration ranges for the protease and bleach individually. A preferred manner of expressing this ratio is [mg active protease per 100 grams of composition/ppm Active Oxygen (ppm Av02) from the peroxyacid in the wash liquor] and will be referred to as the Enzyme to Bleach ratio (E/B ratio). The preferred range for the ratio of active protease to peroxyacid Avθ2 (E/B) is from about 1 to about 20. C. Detergent Surfactant

The compositions of this invention also include from about 1 to about 40 weight % of peroxyacid-stable, water-soluble detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytlcs, and mixtures thereof. From about 2 to about 25 weight % of detergent surfactant is preferred and from about 5 to about 15 weight % is most preferred. Anionic surfactant is preferred and salts of Cn-13 linear alkyl benzene sulfonate, C12-I6 alkyl sulfate and/or methyl ester sulfonates are more preferred. From about 2 to about 25 wt. % of sodium C12-13 linear alkyl benzene sulfonate and sodium C14-15 alkyl sulfate are most preferred.

Detergent surfactants useful herein are listed in U.S. Patents 3,664,961, Norris, issued May 23, 1972, and 3,919,678, Laughlin et al, issued December 30, 1975, both incorporated herein by reference. The following are representative examples of detergent surfactants useful in the present compositions.

Water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cs-Ciβ carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-13LAS.

Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid onoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12. carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful in the compositions of the invention. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene 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.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 15 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol .

Preferred nonionics are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 4 to 8 moles of ethylene oxide per mole of alcohol.

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms. A pholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms. D. Optional Deteroencv Builder

From 1 to about 80, preferably about 20 to about 70, weight % of detergency builder can optionally be, and preferably is, included herein. Inorganic as well as organic builders can be used.

Inorganic detergency 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 aluminosili- cates. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions (hereinafter, collectively "borate builders"), can also be used. Preferably, non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50*C, especially less than about 40'C.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference. However, other silicates may also be useful.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders include those having the empirical formula:

M_z(zAlθ2-ySiθ2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCθ3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders which have the formula:

Na_z[(Alθ2)_z (Siθ2)y]-xH2θ 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. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.

Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.

Organic detergent builders preferred for the purposes of the present invention include polyearboxylate compounds which have a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarbox late builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

One important category of polycarboxylate builders encompasses the ether polycarboxylates. Examples of useful ether polycarboxylates include 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, both of which are incorporated herein by reference.

A specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:

CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -0-CH(C00X)-CH2(C00X); and X is H or a salt-forming cation. Suitable examples of these builders are disclosed in 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, all of which are incorporated herein by reference.

Other useful detergency builders include the ether hydroxypolycarboxylates and the copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.

Also included are polycarboxylates such as ellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders which can also be used in granular compositions.

Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.

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, incorporated herein by reference. Useful succinic acid builders include the C5-C20 alk l succinic acids and salts thereof. The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo- hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water- soluble polyacrylates, and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal car- boxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference.

Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids, and soluble salts thereof, having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of C10-C20 are typically utilized. The hydrocarbyls can be saturated or unsaturated.

Preferably the detergency builder herein is selected from the group consisting of the salts, preferably the sodium salt, of carbonate, silicate, sulfate, phosphate, aluminosilicate, and citric acid and mixtures thereof. E. Second Enzv e

Optional, and preferred, ingredients include second enzymes, particularly peroxidase, cellulase, and mixtures thereof. By "second enzyme" is meant one or more enzymes in addition to protease which are also added to the composition.

The amount of second enzyme used in the composition varies according to the type of enzyme and the use intended. In general, from about 0.0001 to about 1.0, more preferably about 0.001 to about 0.5, weight % of the composition on an active basis of these second enzymes are preferably used.

Purified or nonpurified forms of these enzymes may be used. Enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. F. Other Ingredients

Other ingredients suitable for use in the present compositions, such as water, perfume, brightener, conditioners such as fumed silica, polyethylene glycol, dyes and colorants, and peroxyacids, can be included. Preferred ingredients are from about 0.5 to about 5 wt.% of the composition of polyethylene glycol (preferably with molecular weight between 5,000 and 10,000, most preferably 8,000), from about 0.01 to about 0.7 wt.% of fluorescent whitening and/or brightening agents, and from about 0.01 to about 1.0 wt.% of perfume.

The detergent compositions of the present invention do not need to contain quaternary ammonium salts to delay active oxygen production or to achieve suitably high levels of active oxygen in bleaching solution. Accordingly, such compositions may be substantially free of quaternary ammonium salts.

The granular detergent composition is added to the wash, usually at levels of 1/4 to 1 cup.

This invention most preferably provides a nonphosphate granular laundry detergent composition comprising, by weight of the composition: a. from about 2 to about 7 weight % of nonanoyloxybenzenesulfonate (NOBS) and from about 2 to about 7 weight % of sodium perborate; b. from about 0.096 to about 0.32 of active Protease C per gram of composition; and c. from about 2 to about 25 weight % of sodium C12-13 linear alkyl benzene sulfonate and sodium C14-15 alkyl sulfate.

This invention further provides a method for cleaning fabrics in the wash by contacting the fabrics with a wash solution which contains an effective amount of the detergent compositions hereinbefore described. Agitation is preferably provided in the washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of the granular detergent composition in the washing machine is preferably from about 500 to about 7000 pp , more preferably from about 1000 to about 3000 ppm.

The following examples illustrate the compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

All parts, percentages and ratios used herein are by weight unless otherwise specified.

EXAMPLE I

The wash performance of several proteases are evaluated in the presence of a n-nonanoyloxybenzenesulfonate (N0BS)/sodium perborate (PB1) bleach system in non-phosphate detergent granules prepared according to the following composition: Material Wt.%

Sodium Cπ-13 linear alkyl benzene sulfonate 15.33 Sodium Ci4-i5 alkyl sulfate 6.57

Sodium aluminosilicate 31.52

Sodium carbonate 12.93

Sodium sulfate, moisture, and miscellaneous 30.92

The following proteases are added to the bleach-containing detergent granules at a level of 64 mg active enzyme per 100 gram of product: Maxacal^® ex IBIS; a triple variant of an alkaline serine protease from Bacillus in which tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274 (described in EP 90915958:4) hereinafter referred to as Protease C; and a variant of Protease C hereinafter referred to as Protease CI.

The bleaching performance of n-nonanoyloxybenzenesulfonate and the enzymatic performance of protease are determined in a series of experiments comparing the fabric whitening and stain removal of a treatment containing alkaline detergent granules (composition above) alone, with a treatment containing the detergent granules plus peroxyacid, with a treatment containing detergent granules plus protease, with a treatment containing detergent granules plus peroxyacid plus protease.

Thus, to each of four top-loading automatic washing machines is added 5 lbs. of naturally soiled ballast fabrics and 64 liters of 95^*F city water having a hardness of 6 gr/gal. To one machine is added 87 g of detergent granules only. To the second machine is added 87 g of detergent granules and sufficient N0BS/PB1 to result in an available oxygen (Avθ2) level of 4.2 ppm in the wash solution. To the third machine is added 87 g detergent granules and protease at a level of 64 mg of active enzyme per 100 g of the final product. To the fourth machine is added 87 g detergent granules and the same amount of bleach and protease as in the second and third machine, respectively. The E/B ratio for each of the treatments is 15.2.

To each of the above wash solutions is added two sets of naturally soiled white fabrics and two sets of artificially stained swatches. The washing machines are then allowed to complete their normal washing and rinsing cycles, and the ballast and test fabrics are dryer dried. This procedure is repeated four times, using different sets of ballast fabrics, naturally soiled white fabrics and artificially stained swatches for each replicate.

After completion of the four replicates, the fabrics and swatches are arranged under suitable lighting for comparison of soil and stain removal. Three qualified graders compare the extent of removal of the soils and stains using the following scale:

0: no difference between two swatches

1: thought to be a difference

2: certain of a difference

3: certain of a large difference

4: certain of a very large difference

By this grading the naturally soiled white fabrics are compared for improvement in whiteness, and the artificially stained swatches are compared for removal of the stain. The grades obtained are then averaged and normalized to yield the results. The wash performance data on grass stain is shown in

s * statistically significant difference (confidence level of 95%) relative to all other treatments.

This data shows unexpected synergy between bleach and protease on cleaning of grass stain. All the proteases tested exhibited more performance benefit than the added single contributions of bleach and protease would predict, as Table 1A shows.

Table 1A S±C fi Maxacal^® 3.88 4.25s Protease C 3.59 4.20s Protease CI 3.04 4.04s

ζXAMPlζ π In this example, proteases at a level of 32 mg active enzyme per 100 g of the bleach-containing detergent product are tested as in Example I. The E/B ratio for these treatments is 7.6. Once again, an unexpected synergy exists between bleach (N0BS/PB1) and protease on grass stain. The results are shown in Table 2. b1e

s *^•*^» statistically significant difference (confidence level of 95%) relative to all other treatments.

Table 2A B+C Q Maxacal^® 3.78 4.57s Protease A 3.57 4.04s Protease B 3.85 4.43s

Table 2A shows that, according to this wash performance test, the bleach + protease sample (D) performs significantly better than the added single contributions of the bleach sample (B) and the protease sample (C) for the proteases tested.

EXAMPLE III Several proteases were tested in the presence of different bleach systems in the same detergent composition as Example I. Protease C at a level of 32 mg active enzyme per 100 g of the final product is tested in the presence of benzoyloxybenzenesulfonate (B0BS)/PB1 and tetra acetyl ethylene diamine (TAED)/PB1 bleach systems (E/B ratio of 7.6). Protease C is also tested at a level of 6.4 mg active enzyme per 100 g of the final product in the presence of the nonyl amide of monoperoxy adipic acid (NAPAA) (E/B ratio of 1.5). Protease CI is evaluated in the presence of NAPAA at a level of 64 mg active enzyme per 100 g of the product (E/B ratio of 15.2). In this testing, a sufficient amount of bleach is added to result in an available oxygen level of 4.2 ppm. Performance data on grass stain is presented in Table 3. le

s - statistically significant difference (confidence level of 95%) relative to all other treatments.

The data shows that an unexpected synergy exists between bleach and protease under these conditions, except for the TAED/PB1 bleach system.

Table 3A B±C Q Maxacal^®/BOBS 1.57 2.08s Protease C/TAED 2.44 2.31 Protease C/NAPAA 3.30 3.68s Protease Cl/NAPAA 2.80 3.14s

Table 3A shows that, according to this wash performance test, the bleach and protease sample (D) performs significantly better than the additive contributions of the bleach sample (B) (except TAED) plus the protease sample (C) for the proteases tested.

EXAMPLE IV Protease C is tested at a level of 12.8 mg active enzyme per 100 g of the product (same procedure and same detergent composition as in Example I) in a reduced N0BS/PB1 level (2.7 ppm AvO) and at a lower temperature. The E/B ratio for this example is 4.7. The wash performance is carried out at 70"F and 8 gr/gal hardness. The results are reported in Table 4.

Table 4 Treatment and Average Relative Grade

A s ς a

No Protease Bleach Protease Bleach +

Stains No Bleach only only Protease

Grass 0.00 1.34 1.28 3.39 s Gravy 0.00 0.00 -0.13 0.74 s Betacarotene 0.00 1.61 -0.50 2.49 s s » statistically significant difference (confidence level of 95%) relative to all other treatments

Once again, the data shows that an unexpected synergy exists between protease and bleach (at this reduced bleach level) on grass, gravy and betacarotene stains as shown in Table 4.

Table 4A shows that, according to this wash performance test, the bleach and protease sample (D) performs significantly better than the additive contributions of the bleach sample (B) plus the protease sample (C).

Other proteases such as Protease B, Maxacal, and BPN' can be interchanged with Protease C. Protease levels can be varied between about 0.064 and about 0.64 mg of active enzyme per gram of composition.

Other bleaching agents can be interchanged with NOBS, such as BOBS, NAPAA, the nonylamide of peroxysuccinic acid (NAPSA), and the phenyl sulfonate salt of 6-nonylamino-6-oxycaproicacid and other NAPAA-like activators. The level of bleaching agent can be varied between about 0.5 and about 20 wt % of the composition. Sodium carbonate peroxyhydrate can be used instead of sodium perborate in an amount between about 0.5 and about 20 weight % of the composition.

EXAMPLE V A composition of the present invention is as follows:

Material Wt % Sodium C11-C13 linear alkylbenzene sulfonate 10.36

Sodium C14-C15 alkyl sulfate 2.96

Sodium C14-C15 alkyl ethoxy sulfate 1.48

Sodium aluminosilicate 21.30

Sodium carbonate 25.30

Citric acid 3.00

Sodium n-nonanoyloxybenzene sulfonate 4.73

Sodium perborate monohydrate 3.54

Protease C 0.11* Polyethyleneglycol 1.06

Sodium polyacrylate 2.72 Sodium silicate 1.85

Fluorescent whitening agent, moisture, misc. 11.97 ^♦denotes mg of active enzyme per gram of composition

Other bleaching agents can be substituted for NOBS, such as BOBS, NAPAA, and NAPSA (all defined above). Other proteases such as Protease B, Maxacal^® and BPN' can be substituted for Protease C.

EXAMPLE VI

A laundry bar suitable for hand-washing soild fabrics is prepared by standard extrusion processes and comprises the following: Component

C12 linear alkylbenzene sulfonate Phosphate (as sodium tripolyphosphate Sodium carbonate Sodium pyrophosphate Coconut monoethanolamide Zeolite A (0.1-10 micron) Carboxymethyleel1ulose Polyaerylate ( .w. 1400) Sodium n-nonanoyloxybenzene sulfonate Sodium percarbonate Brightener, perfume Protease C

Lipase (as LIP0LASE)^® CaSθ4 MgS04 Water Filler**

^♦denotes mg of active enzyme per gram of composition

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

The detergent laundry bars are processed in conventional soap or detergent bar making equipment as commonly used in the art.

Claims

1. A granular detergent composition which provides especially effective surface cleaning of textiles, which composition comprises:

A. from 0.5% to 20% by weight of the composition of a bleaching agent which is a ^""substantially insoluble organic peroxyacid, the corresponding carboxylic acid of which has a Hydrophilic-Lipophilic Balance value which ranges from 3 to 6.5, preferably from 4.0 to 6.5;

B. from 0.064 to 0.64 mg, preferably from 0.096 to 0.32 mg, of active protease enzyme per gram of composition with said protease enzyme further being present in an amount sufficient to provide a ratio of mg of active protease per 100 grams of composition to ppm theoretical Available 02 of the peroxyacid ranging from 1:1 to 20:1; and

C. from 1% to 40% by weight of the composition of a detergent surfactant selected from anionic, nonionic, ampholytic and zwitterionic surfactants and combinations thereof; preferably from 2% to 20% by weight of an anionic surfactant.

2. A detergent composition according to Claim 1 wherein

A. the organic peroxyacid is selected from 4-nonyl-amino-4-oxoperoxybutyric acid; 6-(nonylamino)- 6-oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid; heptyl sulfonylperpropionic acid; decylsulphonyl perpropionic acid; heptyl-, octyl-, nonyl-, and decyl- sulphonylperbutyric acids; and combinations of said peroxyacids;

B. the active protease enzyme comprises modified bacterial serine protease enzyme obtained from Bacillus subtilis or Bacillus licheniformis;

C. the anionic surfactant is selected from the salts of C11-13 linear alkyl benzene sulfonate, C12-I6 alkyl sulfate, methyl ester sulfonate and combinations of these surfactants; and D. the composition further comprises from 20% to 70% by weight of the composition of a detergent builder.

3. A granular detergent composition which provides especially effective surface cleaning of textiles, which composition comprises

A. a bleaching agent component which comprises from 0.5% to 20%, preferably from 1% to 10%, by weight of the composition of a bleach activator, which activator is present in combination with a peroxygen compound capable of yielding hydrogen peroxide that can react with said activator to form an organic peroxyacid in situ in bleaching solution formed from said composition; wherein i) said bleach activator has a formula selected from 0

II

(I) R-C-L ;

Rδ 0 0

I II II

(II) Rl - N - C - R² - C - L ; and

0 Rδ 0

II I I

(III) Rl - C - N - R² - C - L ;

wherein R is an alkyl group containing from about 5 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from 6 to 10 carbon atoms; Rl is an alkyl group containing from 6 to 12 carbon atoms; R² is an alkylene containing from 1 to 6 carbon atoms; R-*** is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms; and L is a leaving group, the conjugate acid of which has a pK_a in the range of from 6 to 13; ii) the molar ratio of hydrogen peroxide yielded by said peroxygen compound to said activator is greater than 1.5; and iii) the Hydrophilic-Lipophilic Balance value of the carboxylic acid corresponding to the peroxyacid which is formed in situ ranges from 3 to 6.5, preferably from 4.0 to 6.5; and

C. from 1% to 40% by weight of the composition of a detergent surfactant selected from anionic, nonionic, ampholytic and zwitterionic surfactants and combinations thereof, preferably from 2% to 25% by weight of the composition of an anionic surfactant.

4. A detergent composition according to Claim 3 wherein, when the activator has structure I, then in such structure, R is an alkyl group containing from 5 to 12 carbon atoms wherein the longest linear portion of the alkyl chain extending from and including the earbonyl carbon is from 6 to 10 carbon atoms, and L is selected from the group consisting of:

wherein R2 is an alkyl chain containing from 1 to 8 carbon atoms, and Y is --SO-3M+ or --C00-M+ wherein M is an alkali metal, ammonium or substituted ammonium cation.

5. A detergent composition according to Claim 3 wherein, when the activator has structure II or III, then in such structures, the leaving group L is selected from

R3

R3

0 - CH = C - CH = CH2, - 0 - C = CHR*, and - N - S - CH - R4

I I I R3 0 wherein R⁶ is an alkylene, arylene, or alkarylene group containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group.

6. A detergent composition according to Claim 5 wherein in the structures for the leaving group, Y is selected from the group consisting of --SO3-M+, --C00-M+, --SO4-M+, (--N+R'3)X- and 0<-N(R'3), R' is an alkyl chain containing from 1 to 4 carbon atoms, M is an alkali metal, ammonium or substituted ammonium cation, and X is an anion selected from the group consisting of halide, hydroxide, methylsulfate and acetate anions.

7. A detergent composition according to Claim 3 wherein

A. the activator is selected from sodium nonanoyloxy- benzenesulfonate and sodium benzoyloxybenzenesulfonate;

B. the peroxygen compound is selected from sodium perborate and sodium carbonate peroxyhydrate and is present in an amount of from 1% to 10% by weight of the composition;

C. the molar ratio of hydrogen peroxide yielded by the peroxygen compound to the bleach activator is from 2.0 to 10;

D. the active protease enzyme comprises modified bacterial serine protease enzyme obtained from Bacillus subtilis or Bacillus licheniformis;

E. the anionic surfactant is selected from the salts of C11-13 linear alkyl benzene sulfonate, C12-I6 alkyl sulfate, methyl ester sulfonate and combinations of these surfactants; and

F. the composition further comprises from 20% to 70% by weight of the composition of a detergency builder.

8. A granular detergent composition which provides especially effective surface cleaning of textiles, which composition comprises

A. from 1% to 10% by weight of the composition of a substantially insoluble organic peroxyacid bleaching agent selected from the group consisting of 4-nonyl- amino-4-oxoperoxybutyric acid; 6-(nonylamino)-6- oxoperoxycaproic acid; 1,12-diperoxydodecanedioic acid; heptyl sulfonylperpropionic acid; decylsulphony! perpropionic acid; heptyl-, octyl-, nonyl-, and decyl- sulphonylperbutyric acids; and combinations of such peroxyacids, preferably the nonylamide of peroxyadipic acid or 1,2-diperoxydodecanedioic acid;

B. from 0.096 to 0.32 mg per gram of composition of a serine proteolytic enzyme of bacterial origin; and

C. from 2% to 25% by weight of the composition of a detergent surfactant selected from anionic surfactants, nonionic surfactants and combinations thereof.

9. A granular detergent composition which comprises

A. from 1% to 10% by weight of the composition of a peroxygen bleaching compound selected from sodium perborate, sodium carbonate peroxyhydrate and combinations thereof;

B. from 1% to 10% by weight of the composition of a bleach activator selected from sodium nononoyl- oxybenzene sulfonate and sodium benzoyloxybenzene sulfonate;

C. from 0.096 to 0.32 mg per gram of composition of a serine proteolytic enzyme of bacterial origin; and

D. from 2% to 25% by weight of the composition of a detergent surfactant selected from anionic surfactants, nonionic surfactants and combinations thereof.

10. A detergent composition according to Claim 8 or Claim 9 wherein A. the proteolytic enzyme is selected from Savinase®, Maxacal^®, BPN', Protease A, Protease B, Protease C or combinations thereof; and

B. the detergent surfactant is selected from alkali metal linear alkyl benzene sulfonates, alkali metal alkyl ethylene oxide ether sulfates, alkali metal alkyl ethylene oxide ether sulfates, alkali metal alkyl sulfates or combinations of these surfactants.

11. A detergent composition according to any of Claims 8, 9 or 10 wherein the composition further comprises from 20% to 70% by weight of the composition of a detergency builder selected from carbonates, silicates, sulfates, phosphates, aluminosilicates, citrates and combinations thereof.

12. A nonphosphate granular laundry detergent composition according to Claim 9 which comprises a. from 2% to 7% by weight of the composition of nonanoyloxybenzenesulfonate and from 2% to 7% by weight of the composition of sodium perborate; b. from 0.096 to 0.32 mg of active Protease C per gram of composition; and c. from 2% to 25% by weight of the composition of sodium ^c12-13 linear alkyl benzene sulfonate and sodium C14-15 alkyl sulfate.

13. A method for cleaning fabrics in the wash by contacting the fabrics with a wash solution which contains an effective amount of a detergent composition according to any of Claims 1, 3, 8 or 9.