CA2161212A1 - Bleaching compounds comprising peroxyacid activators used with enzymes - Google Patents

Abstract

The present invention relates to laundry detergent composition comprising conventional detergent ingredients, bleaching systems with one or more bleach activators, and one or more types of detersive enzymes. Preferred bleaching activators are amido-derived bleach activators and/or N-acyl caprolactam bleach activators. The invention also relates to methods of using the detergent compositions.

Description

BLEACHING COMPOUNDS COMPRISING
PEROXYACID ACTIVATORS USED WITH ENZYMES
s FELD OF THE INVENTION
0The present invention relates to laundry del~.~,e"~s and methods which employ one or more types of detersive enzymes and a bleaçhin~ system with one ormore bleach activators.

BACKGROUND OF THE INV~NTION
20Various types of detersive enzymes have long been conventionally used in laundry detergents to assist in the removal of certain stains from fabrics. These stains are typically ~esoci~ed with lipid and protein soils. The enzymes, however, haveproven less effective against other types of soils and stains.
It has also long been known that pc.o.~yA~,n ble?-1-Pc are ~ ,L~., for stain 2s and/or soil removal from fabrics, blut that such b'e?~hes are t~ lp~ re d~p~
At a laundry- liquor t~ c~alul~ of 60C, pe.o~e,~ b!e~ s are only partially c~i~c. As the laundry liquor te.llpc.al.lre is lowered below 60C, peroAy~en b'ea^h~s becoll.c relatively ;~ le. As a con~.1~nce, there has been a S~ arnount of industrial l~,seal-,l to develop ble~ t j~ systems which contain 30 an activator that renders Pe.OAYt,~n bl: ~ -I es effective at laundry liquor te.llpelaLIlres below 60C.
Numerous s~ r~s have been ~ 1Ose~ in the art as effective bleach activators. One widely-used activator is tetraacetyl ethylene ~i~rnine (TAED).
TAED provides effective hydrophilic cleAn;~g ~spec~ y on beverage stains, but has 3s lirnited pe.rurll~ance on dingy, yellow stains such as those res~lting from body oils.
Fortunately, another type of activator, such as nonanoylox~b.-l7~nf ,.-1fonate (NOBS) and other activators which generally CGIllpl;Se long chain alkyl moieties, is SUBSTITUTE S~EE~ ~RULE 26) -WO 94/28106 PCT/US94/0!i372 2 ~2 2 hydrophobic in nature and provides excellent pe,~l",ance on dingy stains.
It would seem that a conlbinaLion of enzymes with either hydrophilic or hydrophobic bleach activators, or both, would provide an effective "all-around"
detergent composition which would perform well on most types of soils and stains.
s However, a hindrance to the development of such all-around cleaning compositions has been the discovery that many of the hydrophobic bleach activators developed thus far can promote damage to natural rubber parts used in certain washing m~hines Because of the negative effects on washing m~hine parts, the selection of such detergent-added ble~chin~ systems has been limited. This is especially true for 0 European detergent/bleaches, since many washing machines m~nllf~c.tured in Europe are equipped with key parts, such as sump hoses and motor g~kçtc, made of natural rubber.
Another problem in developing an all-around cleaning composition has been finding a cleaning agent that is effective under heavy soil load conditions. The5 removal of heavy soil levels, especially nucleophilic and body soils, has proven especially difficult for conventional bleaçhin~ systems. Under such ciru~m~t~n~es, conventional activators such as NOBS appear to interact with, and be destroyed by, heavy soil loads before they can optimally provide their intende(l bleaching function.
Still another problem has been the stability of el~y.,.cs, especiall~ lipases and 20 proteases, in the presence of bleaches.
A need, there~-e, exists for a stable d~lelgenl composition which provides effective çle~ pe, rO....~I-ce over a wide variety of soils and stains. Moreover, the d~ l composition should provide effective rle~nin~ pe.Çu,l,.ance without sulJ~anlially tl~.,.~.~g natural rubber m~.hine parts. In addition, the compositions 25 should provide both ble~^hin~ pc,îullllance and enzyme ~le~ , pe,~u""ance.
Without inten~in~ to be limited by theory, it is believed that typical hydrophobic bleach activators undergo a perhydrolysis reaction to form a peroxyacid bleaching agent. However, a typical by-product of the perhydrolysis reaction belween conventional bleach activators and hydrogen peroxide is a diacylperoxide30 (DAP) species. Unfortunately, DAP species derived from hydl~phobic activatorstend to be insoluble, poorly dis,uel~;lJle, oily materials which form a residue which can deposit on the natural lubber m~.hine parts that are exposed to the laundry liquor.
The oily DAP residue can form a film on the natural rubber m~chine parts and promote free radical and peroxide damage to the rubber, which eventually leads to 3s failure of the parts.
By the present invention, it has now been discovered that the class of I"~lophob:c bleach activators derived from amido acids forms hydrophobic amido SUBSTITllT~ SHE~T (R5JLE 26) WO 94/281~6 2 1 6 1 ~ ~ ~ PC~rU594/0537~

peracids upon pelllydlolysis without the production of harmful, oily DAP's. Again, while not intçntlin~ to be limited by theory, it is believed that the DAP's produced by 4 the perhydrolysis reaction of the amido acid-derived bleach activators used herein are insoluble crystalline solids. The solids do not form a coating film; therefore, the s natural rubber parts are not exposed to the DAP's for eYt~n(led periods of time and remain subst~ntiAlly lln-iAmA~ed In addition to the amido acid-derived bleach activators, it has also now been discovered that the class of bleach activators derived from N-acyl caprolactams provide both hydrophilic and hydrophobic bleaching action without the production of 0 harmful DAP by-products.
Additionally, it has also now been discovered that the class of be"zoxazi"-type bleach activators provide effective hydrophobic bleAching action without the production of harmful DAP by-products.
Surprisingly, it has also been discovered that certain enzymes, particularly lipase enzymes, are co"")alible with said classes of bleach activators.
Accordingly, the present invention solves the long-st~n-~ing need for detergent compositions which provide efficient and effective pe~ro",lallce over a wide range of 1eAninf needs by co,.,bil,i"g the cleA~ g actions of enzymes with the hydrophobic cle~ning action of amido derived bleach activators or with the l~ydlophobic and llydlophilic çleAnin~ action of N-acyl caprolactam bleach activators.
The invention also provides efficient and e~i~ivt; d~;le,~,enl compositions for use in washing mA~llines which have parts made of natural rubber, such that the naturalrubber is subsl~n~;Ally ~n~ by the ~le~chin~ system. These and other benefits are secured by the invention, as will be seen he.~ fltl.
2s BACKGROUND ART
U.S. Patent 4,634,551, Burns et al, issued January 6, 1987, discloses amido peluAy~.cid bl~açhing compounds and their p,~-;u,~o,~ which are employed in the present invention. See also, U.S. Patent 4,852,989, Burns et al, issued August 1, 1989. U.S. Patent 5,069,809, Lagelw~ald et al, issued Dec. 3, 1991 discloses thecG~bin~ion of NOBS bleach activators with LIPOLASE, lipase enzymes. See E.P.
Patent 341,947, Lage,~d, et al, ~,~lished November 15,1989 for a discussion of the co"",alil,ility problems of lipase enzyrnes with certain bleaching systems. U.S.
Patent 4,545,784, Sanderson, issued October 8, 1985, discloses the absorption ofactivators onto sodium perborate monohydrate.
SUMMARY OF THE INVENTION
The invention herein provides cle~ning compositions and methods which are safe for use in contact with natural rubber, and which provide not only bleach SUBSTITllTE S~E~T (RUI E 26) wo 94/28106 PCT/US94/05372 pe,~""ance, but also good detersive enzyme stability and pe,ro."~ance.
The present invention encomp~c~çs de~elge"~ compositions comprising an effective amount of one or more types of el~y-l,es and a bleaching system comprising at least about 0.1%, by weight, of a pe,oxygell bleaching compound and at least s about 0.1%, by weight, of one or more bleach activators, wherein said bleach activators are Illembel ~ selected from the group consisting of:
a) a bleach activator of the general formula:

R1--C I R2-C--L, R1 I C--R2-C--L

or mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group 0 co~ il-g from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group CO..~ g from about 1 to about 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group co..~ g from about 1 to about 10 carbon atoms, and L
is a leaving group;
b) benzoxazin-type bleach activators of the general formula:

R4~N,`,CO--R1 wllel~l Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or di~elellL substitupnt~ se1e.,led from E~ halogen, alkyl, alkenyl, aryl, LYLUAYI~ alkoxyl, amino, alkylamino, COOR6 (wherein R6 is H or analkyl group) and carbonyl filnctio~
c) N-acyl caprolactam bleach activators of the formula:
o O Cl--CH2--CH2 `CH2--CH2~

wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group co~ ;ng from 1 to 12 carbons; and d) mixtures of a), b) and c).
Preferably, the molar ratio of hydrogen peroxide yielded by the peroxygen ble~hing compound to bleach activator is greater than about 1Ø Most preferably, the molar ratio of hydrogen peroxide to bleach activator is at least about l .S.
SlJBSTlTUTE SH~ET (Rl)LE 26) 2~12~2 The present invention also encomr~ees detergent compositions comprising an effective amount of one or more types of enzymes and a bleaching system colllpl;~ing at least about 0.1%, preferably from about 0.1% to about 50%, by weight, of a sul s~an~ially insoluble organic peroxyacid having the general formula:
O O O O
Il 11 11 11 R~C IN R2-C--OOH, R1 IN C--R2-C--OOH

wLe~eill Rl, R2, and R5 are as defined for the type a) bleach activator above.
Ple~lled bleach activators of type a) are those wherein Rl is an alkyl group co~ tli...~ from about 6 to about 12 carbon atoms, R2 contains from about 1 to about 8 carbon atoms, and R5 is H or methyl. Particularly plerel.ed bleach 10 activators are those of the above general formulas wherein Rl is an alkyl group cont~ining from about 7 to about 10 carbon atoms and R2 contains from about 4 toabout 5 carbon atoms.
Pl~fe~led bleach activators of type b) are those wherein R2, R3, R4, and R5 are H and R1 is a phenyl group.
The ,~ler~.. ed acyl moieties of said N-acyl caprolactam bleach activators of type c) have the formula R6-CO- wL~,.ei.~ R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group co..~ ;..g from 1 to 12 carbons, preferably from 6 to 12 carbon atoms.
In highly plefe--ed embodimPnt.~, R6 is a member selected from the group consisting of phenyl, heptyl, octyl, nonyl, 2,4,4-LIillleLhylpentyl, decenyl and mixtures thereof.
Other highly plt;relled del~ ;enl compositions are those comprising bleach a~;livalOI~ sele~ted from the group cQ~ ;..g of:
a) a bleach activator of the formula:
O O O O
R~C N R2-C--L, R1 N C--R2-C--L

or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group co.-l~inil-g from 25 about 1 to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group co..l~;..;..P from about 1 to about 14 carbon atoms, R~ is H or an alkyl, aryl, or alkaryl group co..~ from about 1 to about 10 carbon atoms, and L is a leaving group;
- b) a N-acyl caprolactam bleach activator of the formula:

SUBSTITUTE SHEET (RlJ~E 26) WO 94/28106 ~ 12 PCT/US94/05372 Il C--CH2--CH2~
R6--C--N~ ,C H2 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group co,.~ g from about 1 to about 12 carbons; and c) mixtures of a) and b);
s and an enzyme sçlecte~l from the group consisting of SAVINASE, Protease C, and IlliXLul es thereof. Highly pl ert;l ed activators include benzoyl caprolactam, nona-noyl caprolactam, (6-octanamidocaproyl)oxyb~n7enesulfonate, (6-nonallal.lidocaproyl)oxy-ben7enesl-lfQnate, (6-~lec~n~midocaproyl)oxyben7~nes-l1fnnate, and mixtures thereo 0 The pelo~Sygen bleaching compound can be any peroxide source, and is preferably a member selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, sodium peroxide and mixtures thereof.
Plerelled peroxygen bleaching compounds are selected from the group consisting of sodium perborate monohydrate, sodium percarbonate, sodium perborate tetra-hydrate and ll~ ules thereof. A highly pl-erelled per~,xygen bleaching compound is sodium pelc~ ol.~Le.
The amido-derived and caprolactam bleach activators herein can also be used in co.nl)inalion with rubber-safe, enzyme-safe, hydrophilic activators such as TAED, ty-pically at weight ratios of amido-derived or caprolactam activators:TAED in the range of 1:5 to 5:1, pl~;r~lcbly about 1:1.
The compositions and uses herein are effective with all manner of detersive e~yllles~ e.g., members s~iected from the group col.s;sLing of proteases, amylases, lipases, c~ epe~ peroxidases and mixtures thereof. Highly plerwled are lipase 2s el~yllles derived from the fungus Humicola l~nuginQsa optionally as expressed in Aspergillus oryzae as host using art-disclosed genetic engineering techniques. Also highly plt:rt;-led are modified protease bacterial serine protease el~ylnes obtained from R~cillus subtilis~ cillllc lentus or R~Cill--C lichel-i~oll-lis. Said enzymes comprise at least about 0.001%, prere.~bly from about 0.001% to about ~%, of thedeLe-genL compositions.
The invention also encompa~sçs a method for cleaning fabrics comprising cont~cting, preferably with agitation, said fabrics with an aqueous liquor Co~ gsaid detergent composition. The method can be carried out at te.-~pel~L~Ires below about 60C but, of course, is quite effective and is still safe to rubber parts at laundry SUBSTIT~I~E S~IE~T (RULE 26) WO 94/28106 ~ 2 1~ PCT/US94/05372 te,l,~ LLIres up to the boil. The aqueous laundry liquor comprises at least about 300 ppm of conventional detergent ingredients, as well as at least about 25 ppm of bleach activator and at least about 25 ppm of bleaching compound. Preferably, said aqueous liquor comprises from about 900 ppm to about 20,000 ppm of the conventional detergent ingredients, from about 100 ppm to about 25,000 ppm of ble~çhing compound and from about 100 ppm to about 2,500 ppm of said bleach activator.
The conventional detergent ingredients employed in said method comprise from about 1% to about 99.8%, preferably from about 5% to about 80%, of a 0 detersive surfactant. Optionally, detersive compositions can also comprise from about 5% to about 80% of a detergent builder. Other optional detersive ingredients are also encomp~seed by the fully-form~ ted detergent/bleach compositions provided by this invention.
All pe,ce"Lages, ratios and proportions are by weight, unless otherwise specified. All doc~-m~nte cited are incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The detergent compositions employed in the present invention provide effective and Pfficient surface cle~ning of fabrics which thereby removes stains and/or soils from the fabrics. The ble~ching systems in co,l,binalion with one-or more types of enzymes are particularly efficient at removing most types of soils from the fabrics, inr~ 1ing protein and lipid soils, dingy soils, and heavy soil loads, especially from nucleophilic and body soils.
The superior b-'oa~'-;ng/t~ nin~ action of the present compositions is a~ with safety to natural rubber m~eh;rle parts and other natural rubber articles, inrl~-tling fabrics co~ g natural rubber and natural rubber elastic materials. The bl2~chin~ ...cG~ e~ and, in particular, the surface ble~rhing ...ecl-A~ m are not cc"l,lJletely understood. However, it is generally believed that the bleach activator undergoes nucleophilic attack by a pe~hydro~ide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach, to form a pelo~y~,a,l,oxylic 30 acid. This reaction is commonly ,ere"ed to as perhydrolysis.
The bleaching systems and a_~iv~tGr~ herein afford additional advantages in that, unexpectedly, they are safer to fabrics and cause less color damage than other activators when used in the manner provided by this invention.
- It is also believed that the bleach activators within the invention can render 35 pero~ygc;n bleaches more efficient even at laundry liquor temperatures wherein bleach activators are not l-ecess~y- to activate the bleach, i.e., above about 60C.
Th.,.~,role, with bleach systems of the invention, less pero~y~;ell bleach is required to SUBSTITUTE SI~EET (RU~E 26) WO 94/28106 ~ 2 PCT/US94/05372 get the same level of surface ble. ching pt;,ro."l&nce as is obtained with the peroxygen bleach alone.
The bleaching systems, wherein the bleach activator is used, also have as an çss~nti~l component a peroxygen bleach capable of releasing hydrogen peroxide in5 aqueous solution.
The Bleach Activator Amido Derived Bleach Activators - The bleach activators of type a) employed in the present invention are amide substituted compounds of the general formulas:
O O O O
R1--C I R2_C--L, R1 N C--R2_C--L
R~ R5 or mixtures thereof, wherein R1, R2 and R5 are as defined above and L can be ç~nti~lly any suitable leaving group. A leaving group is any group that is displaced from the ble~ching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the pe,l,ydrolysis reaction, results in the formation of the pelo~yc~l)oxylic acid. Generally, for a group to be a suitable leaving group it must exert an CIC~LI on attracting effect. It should also form a stable entity so that the rate of the back reaction is negligible. This f~cilit~tes thenucleophilic attack by the p~Lyd~u~ide anion.
The L group must be sufficiently reactive for the reaction to occur within the 20 opl"~,u"~ time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a ~leP-hir~ composition. These ch~clt~istics 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 in which their conju~te acid has a pKa in the range 2s of from about 4 to about 13, preferably from about 6 to about 1 1 and most preferably from about 8 to about 11.
~le~"ed bleach activators are those of the above general formula wherein Rl, R2 and R5 are as defined for the pero~cid and L is selected from the group CQ~ , of:

Sl JBSTITUTE SHEET (R~ILE 26) WO 94/28106 ~ 212 PCT/US94/05372 --0~, O~Y , and --~

R3 L~ R3 Y
y -O--CH=C--CH=CH2 --O--CH=C--CH=CH2 O ~CH2~ $NR4 O O

IR3 o r --O--C=CHR4 , and N '--CH--R4 l3 o s and mixtures thereof, wherein R1 is an alkyl, aryl, o~ alkaryl group co..~ -g from about 1 to about 14 carbon atoms, R3 is an alkyl chain co..~ from 1 to about 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
The p~ -lt;d solubilizing groups are -SO3 M+, -C02 M+, -SO4 M+, -N (R3)4X and o<--N~R3)3 and most pl~r~l~bly -SO3 M+ and -C02 M whereino R3 is an alkyl chain CO~ g from about 1 to about 4 carbon atoms, M is a cationwhich 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 substit~lted a"",-onium cation, with sodium and potassium being most prc;re"~d, and X is a halide, hydroxide",~ l,yl~,llfate or acetate anion. It should be noted that 5 bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
Pl ere" ed bleach activators are those of the above general formula wherein L
is selected from the group consisli,lg of:

SUBSTITl ITE S~JEET (RIJ~E 26) W0 94/28106 ?,~ ~?~ o PCT/US94/05372 --0~ --O~Y , and --0~

wherein R3 is as defined above and Y is -S03-M+ or -C02-M+ wLc;leill M is as defined above.
Another important class of bleach activators, inr.lu~ing those of type b) and s type c), provide organic peracids as described herein by ring-opening as a con~equçnce of the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion. For in~t~n~e, this ring-opening reaction in type c) activators involves attack at the caprolactam ring carbonyl by hydrogen peroxide or its anion.
Since attack of an acyl caprolactam by hydrogen peroxide or its anion occurs o preferably at the exocyclic carbonyl, obtaining a significant fraction of ring-opening may require a catalyst. Another example of ring-opening bleach activators can befound in type b) activators, such as those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
Such activator compounds disclosed by Hodge include the activators of the 5 ben70Y~7in-type, having the formula:

C

in~ ii~ the substit~ted b~ ,u~ u ofthe type F~R34~ "C--R

wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may 20 be the same or dirre,t;..l substituçnts s~lected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (whe-ein R6 is H or an alkyl group)and carbonyl functions.
A pl~re--ed activator ofthe benzoxazin-type is:

SlJBST~TUT~ SHEET (RULE 2~) WO 94/28106 2,16 1 2 12 PCT/US94/05372 N ~
When the activators are used, optimum surface bleaching pelrolll.ance is obtained with washing solutions wherein the pH of such solution is between about8.5 and 10.5 and preferably between 9.5 and 10.5 in order to f~ilit~te the 5 perhydrolysis reaction. Such pH can be obtained with substances commonly knownas buffering agents, which are optional components of the bleaching systems herein.
The N-Acyl Caprolactam Bleach Activators - The N-acyl caprolactam bleach activators of type c) employed in the present invention have the formula:
o R6--C--N~ ~CH2 o wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group cont~ining from 1 to 12 carbons. Caprolactam activators wherein the R6 moiety COII~illS at least about 6, preferably from 6 to about 12, carbon atoms provide hydrophobic bleaching which affords nucleophilic and body soil clean-up, as noted above. Caprol~ct~m activators ~llelt;in R6 comprises from 1 to about 6 carbon atoms provide hydrophilic bleaçhin~
species which are particularly efficient for bleachin~ beverage stains. Mixtures of llydl~phobic and hydrophilic caprol~ct~m~, typically at weight ratios of 1:5 to 5:1, plef~,.~ly 1:1, can be used herein for mixed stain removat benefits.
Highly pl~;rellel N-acyl capro~ m~ are s~olected from the group con;,l~lil,g of benzoyl caprolrct~m octanoyl caprolactam, nonanoyl caprolactam, 3,5,5-L~ime~Lylhexanoyl caprolactam, decanoyl caprolactam, lln-iecçnoyl caprolactam, and mixtures thereof.
Methods for making N-acyl capro!act~m~ are well known in the art.
F.Y~mp~ . I and II, incl~lded below, illustrate p,t;relled laboratory synt~lesesContrary to the t~fl~ of U.S. Pat. 4,545,784, cited above, the bleach 25 activator is pl~e,ably not absorbed onto the peio~y~sell bleaching compound. To do so in the presence of other organic detersive ingredients could cause safety problems.
The bleach activators of type a), b) or c) will comprise at least about 0.1%, p.er~ bly from about 0.1% to about 50%, more plt;rt;rably from about 1% to about30%, most p,efe,~bly from about 3% to about 25%, by weight of bleaching system or de~e,~en~ composition.

SUBSTITUT~ SHEET (RULE 26) 7~ ~ 12 When the activators are used, optimum surface bleaching performance is obtained with s~ t~ ns 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 f~cilit~te the perhydrolysis reaction. Such pH can be obtained with substances commonly known s as buffering agents, which are optional components of the ble~ching systems herein.
The Pe~oxy~en Bleaching Compound The peloxygen bleaching systems useful herein are those capable of yielding hydrogen peroxide in an aqueous liquor. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide o bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
Preferred peroxygen bleaching compounds include sodium perborate, 5 co,l""elcially available in the form of mono-, tri-, and tetra-hydrate, sodiumpyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, and sodiumperoxide. Particularly p,erti"ed are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Percarbonate is especially l)lere~t;d because it is very stable during storage and yet still dissolves very quickly in the bleaching 20 liquor. It is believed that such rapid dissolution results in the forrnation of higher levels of percarboxylic acid and, thus, enh~nced surface bleaching 1)~l ful "~ance.
Highly plefelled percarbonate can be in uncoated or coated form. The average particle size of lmcoated p.,..,~ nale ranges from about 400 to about 1200 microns, most p.~fe.~bly from about 400 to about 600 microns. If coated 2s percarbonate is used, the p,ere.,ed coating materials include I~UIeS of ca~l~or~ale and sulphate, silicate, borosilicate, or fatty carboxylic acids.
The pero~yge" bleaçhing compound will comprise at least about 0.1%, preferably from about 1% to about 75%, more preferably from about 3% to about 40%, most ~,efe,ably from about 3% to about 25%, by weight of ble~çhing system 30 or detergent composition.
The weight ratio of bleach activator to peroxygen ble~rlling compound in the bl~aching system typically ranges from about 2:1 to 1:5. Plefel,ed ratios range from about 1:1 to about 1:3.
The bleach activator/bleaching compound systems herein are usefill per se as 3s bleaches. However, such ble~çhing systems are especially useful in compositions which can CO~ l;SC various detersive adillncts such as surf~ct~nt.c, builders and the like.

SIJ~STITU~E SH~ET (RULE 26) WO 94/28106 ~, ~. 6 1 2~ 12 PCT/US94/05372 The Detersive Enzymes The detersive enzymes of the present invention are included for a wide variety of fabric laundering purposes, inell~lin~ removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of fugitive dye ~,al,~rer. The enzymes to be incorporated include proteases, amylases, lipases, cçll~ ses, and peroxid~qes, as well as mixtures thereo Other types of enzymes may also be in~.lude(~ They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by severalfactors such as pH-activity and/or stability optima, thermostability, stability versus 0 active de~el~ e.,ls, builders and so on. In this respect bacterial or fungal enzymes are pr~r~" ed, such as bacterial amylases and proteases, and fungal c~ ces.
Enzymes are normally incorporated at levels sufficient to provide up to about 50 mg by weight, more typically about 0.01 mg to about 10 mg, of active enzyme per gram of delelgenl composition. Stated otherwise, an effective amount of the enzymes employed in the present invention will comprise at least about 0.001%, plefe,ably from about 0.001% to about 5%, more preferably from about 0.001% to about 1%, most preferably from about 0.01% to about 1%, by weight of detergent co",pos,Lion.
Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis, B.lentus and B.licheluro,,ns. Another suitablep,utcase is a mo~ified bacterial serine protease enzyme obtained from Rp,cill~lcsubtilis or R~ S lichelurulll~s~ having m~ximl-m activity throughout the pH range of 8-12, d~eloped and sold by Novo Industries A/S under the r~i~leled trade nameESPERASE. The p,~p~lion ofthis enzyme and an~logous e.~".~,s is described in 2s British Patent Spe~ ;~c~;on No. 1,243,784 of Novo. Proteolytic Cl~,~ eS suitable for removing protein-based stains that are co"u~lcially available include those soldunder the traden~mes ALCALASE and SAVINASE by Novo Industries A/S
~Delù,.a,k) 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, f~led April 28, 1987, and Eulopeall Patent Application 130,756, Bott et al, published January 9, 1985). Most p,t;r~"ed is what is called herein "Protease C", which is a variant of an alkaline serine protease from R~c.ill~c particularly Bacillus lentus~ in which arginine replaced Iysine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced llu~on,l-e at position 274. Protease C is described in EP
90915958:4, U.S. Patent No. 5,185,250 and U.S. Patent No. 5,204,015, which are SUBSTITUTE S5 IEET (Rl)L~ 26) -wo 94/28106 ~16 ~ 14 PCT/uSg4/ns37 incorporated herein by reference. Genetically modified v~lianls, particularly ofProtease C, are also incl~lded herein.
Amylases include, for example, a-amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc.5 and TERMAMYL, Novo Industries.
The cPll~ ees usable in the present invention include both bacterial or fungal c~ ee Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cell~ es are disclosed in U.S. Patent 4,435,307, Ball,esgoald et al, issued March 6, 1984, which discloses fungal cellnl~ee produced from Humicola insolens and Humicola strain DSM1800 or a cPll~ ee 212-producing fungus belonging to the genus Aeromonas, and celllll~ee extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable celllll~ees are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Suitable lipase enzymes for detergent usage include those produced by microorg~nieme of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in J~p~nP,se Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano PLal~ ceutic~l Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," heleinanel lc;rell~d to as "Amano-P." Other 20 co....~ cial lipases include A-m--ano-cEs~ lipases ex Chromobacter viscosum, e.g.
Chlolllobacter viscosum var. Iipolyticum NRRLB 3673, commercially available fromToyo Jozo Co., Tagata, Japan; and further Chrom~b~ct~Pr viscosum lipases from U.S.
BiochPm:c~l Corp., U.S.A. and Disoynth Co., The Nell~ ds~ and lipases ex Pseudomon~e gladioli. The LIPOLASE enzyme, derived from the fungus Humicola 2s l~nu~inosa and ~,A~ressed in Asper~illus oryzae as host and colll~ ;ally available from Novo (see also E.P. Patent 341,947) is a ~ lled lipase for use herein.
Peroxidase el~yllles are used in colllb,-lalion with oxygen sources, e.g., pelcall,onale, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution b'e~ching " i.e. to prevent llal~ of dyes or p,g...~ s removed from sub-30 strates during wash operations to other ~ubs~lales in the wash solution. Peroxidaseel~yllles are known in the art, and include, for example, horseradish peroxi~ee~
ligrin~eP, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-co~ g detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, ~esi~ned to 35 Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation into ,eynthetic detergent granules is also disclosed in U.S. Patent 3,5~3,139, issued SUBSTITUTE SHEET (RULE 26!) WO94/28106 ~,~6'~2 PCT/US94/05372 January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formu!ations, and their inco~,ol~ion into such formulations, are disclosed in U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in de~elge-,Ls can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0199405, Application No. 86200586.5, published 0 October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
Enzyme Stabilizers - The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium ions in the finished compositions which provide calcium ions to the enzymes.-~ Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S. 4,537,706, cited above. Typical delelgenls, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about S to about 15, and most prere;-~bly from about 8 to about 12, millimoles of ç~lcillm ion per liter of fini~hed composition. This can vary somewhat, depen(~ing on the amount of enzyme present and its response to the calcium ions.The level of calcium ion should be sPlected so that there is always some minim-lm level available for the enzyme, after allowing for co",~ Y~tif.n with builders, fatty acids, etc., in the co"~l,G;,;lion. Any water-soluble calcium salt can be used as the source of c~lri~lm ion, inr.1~1rii~ but not limited to, c~lci~m chloride, c~ m sulfate, 2s cs~ malate, calcium hydroxide, calcium fc"",ale, and ç~lr;~-m acetate. A small amount of c~lri~.m ion, generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water. In solid detergent compositions the formulation may include a sllfficientquantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water har~ncss may suffice.
The co"")osilions herein may also optionally, but preferably, contain various additional stabilizers inr.lur1ing silicate coatings and, especially borate-type stabilizers.
Typically, such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from 3s about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
Boric acid is pr~ ed, ~ltho~lgh other co,~",o~mds such as boric oxide, borax and SUBST~TUTE SH~ET (RULE 26) WO 94/28106 PCT/US94/05372 a 2~ ~ 16 other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boricacid.
Detersive Surfactant The amount of detersive surfactant inr,l~lded in the fully-form~ ted detergent compositions afforded by the present invention can vary from about 1% to about 99.8% depending upon the particular surfactants used and the effects desired.
Pl~r~;,ably, the detersive surf~ct~nte co""u,ise from about 5% to about 80% by 0 weight of the detergent ingredients.
The detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surf~r,t~nt~ can also be used. Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic surfAct~nts with other su, rA~ c, especially nonionic surf~ct~ntc Nonl;.. ;l;,.g examples of surf~ct~nt~ useful herein include the conventionalCl1 C18 alkyl benzene sulfonates and primary, secondary, and random alkyl sl-lf~te~
the C10-C18 alkyl alkoxy s--lf~te~, the C10-C18 alkyl polyglycosides and their col,es,oonding s~lf~ted polyglycosides, C12-C18 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkyl phenol alkoxylates (especi~lly ethoxylates and mixed etho~y/propuxy), C12-C18 b~tailles and sulfobetaines (~'s~lt~ines~ C10-C18 amineoxides, and the like. Other conventional useful surfactants are listed in standard texts.
One particular class of adjunct no~ surf~ct~nt~ especially useful herein co"""ises the pol~ dl~ fatty acid amides ofthe formula:
o R1 25 ( ) R2-C--I--Z
wherein: Rl is H, Cl-C8 hydrocarbyl, 2-hydlo~elhyl~ 2-hydLo~ylJIolJyl, or a mixture thereof, prefer~ly C1-C4 alkyl, more preferably C1 or C2 alkyl, most pr~,ably Cl alkyl (i.e., methyl); and R2 is a C5-C32 hydrocarbyl moiety, prt;re,~bly straight chain C7-Clg alkyl or alkenyl, more p,ere,~bly straight chain Cg-C17 alkyl 30 or alkenyl, most prerel~bly straight chain Cll-Clg alkyl or alkenyl, or ,nixture 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 red~cin~ sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z prere, ~Iy will be derived from a 35 r~ ring sugar in a reductive ~min~tion reaction; more pre~lably Z is a glycityl SUBSTITUTE SHEET (RU~E 26) ~161212 WO 94/28106 PCT/US9~/05372 moiety. Suitable re~llring sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means inten-led to exclude other suitable raw materials. Z preferably will be s~lected from the group consisting of -CH2-(CHOH)n-CH2OH~-CH(CH2OH)-(CHOH)n 1--CH2OH,-CH2 -(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated 0 derivatives thereof. Most prefel, ~d are glycityls wherein n is 4, particularly -CH2-(CHOH)4CH20H.
In Formula (I), R 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 sll-l.cin~ Rl is preferably methyl or hydroxy-alkyl. If lower sudsing is desired, Rl is prere.~ly C2 C8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethyl hexyl.
R2-CO-N< can be, for example, coc~mide, ~lea~ ide~ oleamide, lauramide, ................................ .yl.~ e~ capric~m:de, p~lmit~m;~1e, tallowamide, etc.
Detersive Builders Optional detergent ingredients employed in the present invention contain inolganic and/or organic detersive builders to assist in mineral hardness control. If used, these builders comprise from about 5% to about 80% by weight of the delt~ co~lyo~ ons.
~organic d~,t~ e l,~lildt; ~ inr~lvd~, but are not limited to, the alkali metal,O~ m and alkanolh~ u~ -.. salts of polyphosphates (~ pl;l~ed by the tri-polyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phos-pho~ ec phytic acid, silicates, C~lbOndlCS (;nCI~d;ng bicarbonates and sesqui-call,onales), s -lph~tç5, and ~lllminosilicates. However, nonphosphate builders are required in some locales.
Exa~lples of silicate builders are the alkali metal silic~tçs particularly thosehaving a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and iayered silic~te~, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, available from Hoechst under the trademark "SKS"; SKS-6 is an especially plerellt;d layered silicate builder.
3s Carbonate builders, especially a finely ground calcium carbonate with surface area greater than 10 m2/g, are preferred builders that can be used in granular compositions. The density of such alkali metal carbonate built deLe.ge..Ls can be in Sl~BSTITUJE SHEET (~U~E 2~) -WO 94n81~6 1 6 1 ~ 1 2 18 PCT/U594/0537 the range of 450-850 g/l with the moisture content preferably below 4%.
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.
~ minocilicate builders are especially useful in the present invention.
P~ere~led ~ minQsilicates are zeolite builders which have the formula:
Naz[(Al02)z (SiO2)y] XH2 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.
0 Useful ~lllminosilicate ion exchange materials are commercially available.
These ~lllminQsilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. Methods for producing ~lllminosilicate ion exchange materials are disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 197~, and U.S. Patent 4,605,509, Corkill, et al, issued Aug. 12, 1986. Preferred synthetic crystalline ~lumint~silicate ion e~ch~nge materials useful herein are available under the dtocign~tions Zeolite A, Zeolite P (B) (in~ riing those disclosed in EPO 384,070), and Zeolite X. Preferably, the ~lllminocilic?~te has a particle size of about 0.1-10 microns in tli~m~ter.
Organic detersive builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds, such as ether polyca,l,u~ylates, in~ oxy-iicuc~in~te~ 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. Sl~it~hle ether polycs~l/u~.ylates also include cyclic 25 co,pom~ds, particularly alicyclic compounds, such as those des~i.il,ed in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detersive builders include the ether hydroxy-polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydro~y benzene-2, 4, 6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, the various alkali metal, ammonium and subs~ ed ammonium salts of polyacetic acids such as ethylene~ e tetraacetic acid and nitrilotriacetic acid, as well as polyca,l,l)~ylates such as mellitic acid, sucçinic acid, oxydicucçinic 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 p,e~,~ed polycarboxylate builders that can also be used in granular co...~osilions, especiqlly in co.nl,h~dlion with zeolite and/or layered silicate builders.

S~ST~TUTF ~HEET (RULE 26) ~ WO 94/28106 21~12 ~ ~ PCT/US94/05372 Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy ~1-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
Patent 4,566,984, Bush, issued January 28, 1986.
In situations where phosphorus-based builders can be used, and especially in s the formulation of bars used for hand-laundering operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphateand sodium orthophosphate can be used. Phosphonate builders such as ethane-l-hydroxy-1,1-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 0 used.
Optional Detersive Adjuncts As a prere"ed embodiment, the conventional detergent ingredients employed herein can be s.olected from typical detergent composition components such as detersive surf~ct~nts and detersive builders. Optionally, the detergent ingredients can include one or more other detersive adjuncts or other materials for ~c.cicting or enh~nc.ing cle~ning p~,.rJ".-ance, Ll~ of the substrate to be cle~nerl, or to modify the ~e.sthetiç,c of the detergent composition. Usual detersive adjuncts of dt;le~,e"l compositions include the ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al, are incorporated herein by reference. Such adjuncts which can be in~ ded in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to about 20% of the detel~"l ingredients, pr~,fer~bly from about 0.5% ~o about 10%), include color s~.P~les, suds boosters, suds .7Up~lt;Ss~l.7, allli~uis7h and/or anticorrosion agents, soil~ s~ .3 agents, soil release agents, dyes, fillers, optical bli~hl~ .7, 2s germicides, ~ linity sources, h~drollo~,es, ~ntioxitl~ntc~ p~.rul~es, solvents, solubilizing agents, clay soil removal/anti-redeposition agents, polymeric dis~ ,ing agents, processing aids, fabric sollelung components static control agents, etc.Bleach systems optionally, but preferably, will also cG",~,ise a chelant which not only Pl~hAncçs bleach stability by scavenging heavy metal ions which tend todcco",?ose ble ? ^h~c, but also assists in the removal of polyphenolic stains such as tea stains, and the like. Various çhPl~"l~; inclu~in~ the &lninophosphQI-~lec, available as - DEQUEST from ~onC~nto' the nitrilotri~cet~tP-c~ the Lydlo~yt;ll~l-ethylç~e~ ;lle triAcet~teC, and the like, are known for such use. Plt;r~lled biodegradable, non-phosphorus çh~l~nt.c include ethylene~ min~ tlic~1cçin~te ("EDDS"; see U.S. Patent 3s 4,704,233, Hartman and Perkins), ethylene~iAmine-N,~-digl~lt~mAte (EDDG) and 2-hydroxypropylenedi~.nil-e-N,N'-tiic~lcçin~te (HPDDS) compounds. Such çhel~ntc can be used in their aLkali or alkaline earth metal salts, typically at levels from about SUBSTITUTE SHEET (RIJLE 26) 2i2 20 0.1% to about 10% ofthe present compositions.
Optionally, the detergent compositions employed herein can comprise, in addition to the ble~chin~ system of the present invention, one or more other conventional ble~ching agents, activators, or stabilizers which do not react with or 5 otherwise harm natural rubber. In general, the formulator will ensure that the bleach compounds used are compatible with the d~er~,e"~ formulation. Conventional tests, such as tests of bleach activity on storage in the presence of the separate or fully-form..l~ted ingredients, can be used for this purpose. A specific example of an optional bleaçhin~ agent for incorporation in this invention is tetraacetyl ethylene o diamine (TAED) Such bleaching compounds and agents can be optionally in~ cled in detergent compositions in their conventional art-established levels of use, generally from 0% to about 15%, by weight of detergent composition.
Bleaching activators of the invention are especially useful in conventional laundry detergent compositions such as those typically found in granular detergents or laundry bars. U.S. Patent 3,178,370, Okenfile.~, issued April 13, 1965, describes laundry detergent bars and processes for making them. Philippine Patent 13,778, Anderson, issued Sept. 23, 1980, describes synthetic detergent laundry bars.
Methods for making laundry detergent bars by various extrusion methods are well known in the art.
The following examples are given to further illustrate the present invention, but are not intt~nrled to be limiting thereof.
EXAMPLE I
Sy~ e~is of Nonanoyl Caprolactam - To a two litre three necked round bollomed flask e luipped with a ~on~ , overhead stirrer and 250ml ~tlrlition 2s funnel is chal~,ed 56.6g (0.5 moles) caprolactam, 55.7g (0.55 moles) triet},yl&.,~ine and 1 litre of dio~nt; the resulting solution is heated to reflux (120C). A solution of 88.4g (0.5 moles) nonanoyl chloride dissolved in 200ml of dioxane is then added over 30 mimltes and the mixture is refluxed for a further 6 hours. The reaction mixture is then cooled, filtered, and the solvent removed by rotary evaporation to yield 120.5g of the product as a dark oil. This crude product is then dissolved in diethyl ether, waehed with 3xSOml aliquots of water, dried over m~ eillm s -lrh~te and the solvent removed by rotary evaporation to yield 81.84g (65% theoretical yield) of product which is shown by N~ to be 90% pure, with the r.o,~
material being nonanoic acid.
EXAMPLE II
Synthesis of Benzoyl Caprolactam - To a two litre three necked round bottomed fiask e~lu;pped with a condenser, overhead stirrer and 250ml addition SUBSTITU~E SH~ET (RU~E 26) ~ WO 94/28106 2 1 612 12 PCT/US94/05372 funnel is charged 68.2g (0.6 moles) caprolactam, 70g (0.7 moles) triethylamine and 1 litre of dioxane; the resl-lting solution is heated to reflux (120C). A solution of A 84.4g (0.6 moles) benzoyl chloride dissolved in 200ml of dioxane is then added over 30 minlltes and the mixture is refluxed for a further 6 hours. The reaction mixture is s then cooled, filtered, and the solvent removed by rotary evaporation to yield 121.7g of the product as an oil which cryst~lli7:es on st~n-iing This crude product is then redissolved in toluene and p~e~ aled with hexane, yielding 103g (79% theoreticalyield) of a white solid which which is shown by NMR to be over 95% pure, with the re~ g material being benzoic acid.
EXAMPLE m Synthesis of(6-non~ ..,idocaproyl)oxyb~n7~.nPsl-lfonate (NACA-OBS).
6-nonana"lidocaproic Acid (NACA) - The reaction is carried out in a 12L 3-necked flask equipped with a thermometer, addition funnel and meçh~nical stirrer.
To a solution made from 212g (5.3 moles) of sodium hydroxide and 6L of water (cooled to room te"lpe~lure) is added 694.3g (5.3 moles) of 6-aminocaproic acid.This mixture is cooled to 10C and a solution of 694.3g (5.3 moles) of nonanoyl chloride in lL of ether is added in a slow stream (about 2.5 hours) keeping the te",pe~ re at 10-lSC. During the ~d~itiQn, and subsequently until acidification, the reaction is ...~ ed at pH 11-12 by periodic addition of 50% NaOH. After the 20 addition is complete, the reaction is stirred for another 2 hours at 10C and allowed to come to room tel~pe~Lu~e before acidification to pH 1 with conc. HCI. The preç;~ ed product is vacuum filtered, the filter cake is washed twice with 8L
portions of water and the product air dried o-Je~ l. It is then s..cp~n-led in 3L of hexane, f~ltered and washed with an ~d~lition~l 3L of hexane. The product is then 2s vacuum dried ove .~;l,l (50C, 1 mm) to give 1354 g (94%) of NACA.
Acid Chloride (NACA-CI) - The reaction is carried out in a SL, 3-necked flask equipped with an addition funnel, .~e~lunic~l stirrer and argon sweep. To a suspension of 542g (2.0 moles) of NACA in 2L of toluene is added (in a slow stream over 30 minlltes) 476g (4.0 moles) of thionyl chloride. This mixture is stirred at room tempela~ult: for four hours during which time the solids dissolve. The solution is partially evaporated (30C, 10 mm) to remove any excess thionyl c~loride leaving 905g of NACA-CVtoluene solution (col~Lail~s approA""a~ely 2 moles of NACA-CI).
An IR spectrum COnrll Il~S conversion of COOH to COCI.
(6-nonal1a",idocaproyl)oxybenzenesulfonate (NACA-OBS) - The reactor is a 3s 12L, 3-necked flask equipped with a condenser, mech~nical stirrer and static argon supply. To the reactor are added 647g ofthe above NACA-CI/toluene solution (1.43moles), 6L of toluene and 310.8g (1.43 moles) of disodium p-phenolsulfonate SllBST3TUTE S~IEET (RU~E ~6) 2~ 22 ~ o~ m p-phenolsulfonate is previously p,epaled and dried in a vacuum oven before use (110C, 0.1mm hg, 18 hours). This mixture is refluxed for 18 hours.
After cooling to room te~ c~ re, the product is collected on a Buchner funnel and dried to give 725g of crude solids. The crude is taken up in 7L of rçfl~-xing 87:13 5 (v,v) methanol/water, filtered hot and allowed to rewy~Lallize at room temperature.
The resulting precipitate is filtered and vacuum dried (50C, 0.1 mm) for 18 hours to give 410g (64% based on NACA) of light tan product. A trace of unreacted phenolsulfonate is inrlic~ted by the small doublets at 6.75 and 7.55 ppm in the lH
spectrum. Otherwise, the spectra are consistent with expected structure and no other 0 impurities are evident.
EXAMPLE IV
A granular detergent composition is prepared comprising the following ingredients.
Component Wei~ht %
C12 linear alkyl benzene sulfonate 22 Phosphate (as sodium tripolyphosphate) 30 Sodium carbonate 14 Sodium silicate 3 Lipase 0 3 Sodium percarbonate 5 Ethylene.li~mine di~lcçin~te chelant (EDDS) 0.4 Sodium sulfate ~ 5.5 Nonanoyl caprolart~m 5 Filler* and water R~l~nr,e to 100%
25 *Can be sele~iled from col,~enienl materials such as CaC03, talc, clay, silicates, and the like.
In testing the ble~çhing pe,ro~ ance and effect on natural rubber washing m~chin~ parts, the following test method is used:
Aqueous crutcher mixes of heat and alkali stable components of the detergent 30 compositions are prepared and spray-dried and the other ingredients are admixed so that they contain the ingredients t~b~ ted at the levels shown.
The de~e-ge"L granules with bleach activator are added together with 5 Ib.
(2.3 kg) of previously laundered fabrics inclu~ing natural rubber articles such as elastic materials, to an automatic washing m~rhine equipped with a natural rubber 3s sump hose. Actual weights of deLe,ge"L and bleach activator are taken to provide a 950 ppm conce"L,~lion ofthe former and 50 ppm concentration ofthe latter in the 17 gallon (65 1) water-fill m~rhine The water used has 7 grains/gallon hardness and a SlJBSrlTUTE SHEET (R~ILE 26) ~ WO 94/28106 21 6 ~ 2 1~ PCT/US94/05372 pH of 7 to 7.5 prior to (about 9 to about 10.~ after) addition of the detergent and ble~ching system.
The fabrics are laundered at 35C (95F) for a full cycle (12 min.) and rinsed at 21C (70F). The laundering method is repeated for 2,000 wash cycles without s rupture of, or significant damage to, the natural rubber parts or without damage to the natural rubber conl~ined in the fabrics and with good enzyme performance.
EXAMPLE V
A granular dt;lelg~"l composition is plepaled comprising the following ingredients.
o Component Wei~ht %
Anionic alkyl sulfate 7 Nonionic surfactant 5 Zeolite (0.1-10 micron) 10 Trisodium citrate 2 SKS-6 silicate builder 10 Acrylate maleate polymer 4 Nonanoyl caprolactam 5 Sodium pelca-l,ol-ale* 15 Sodium ca.bonate 5 Ethylçne~i~mine ~ crin~te chelant (EDDS) 0.4 Suds sul)p-~ssor 2 Protease (as SAVINASE) 0.3 Lipase (as LIPOLASE) 0.3 Soil release agent 0.2 Minors, filler** andwater p~ nceto 100%
*Average particle size of 400 to 1200 microns.
**Can be selected from convenient materials such as CaCO3, talc, clay, .cilic~tç~, and the like.
In testing the bleaching pe-ro....ance and effect on natural rubber washing 30 "n~ c parts, the following test method is used:
~q~eo-l~ clulcher mixes of heat and alkali stable components of the del~.gc;..l co.. ,posilion are prepared and spray-dried, and the other ingredients are ~f~mixed so that they contain the ingredients tabulated at the levels shown.
The detergent granules with bleach activator are added via the dispensing 35 drawer together with ~ Ib. (2.3 kg) of previously laundered fabrics to an automatic washing m~r.hin~ equipped with a natural rubber sump hose. Actual weights of deler~e..l and bleach acli~alor are taken to provide a 8,000 ppm cQnr~çntration of the SUBSTITUT~ SHEET ~RULE 26) ~1212 ~

former and 400 ppm conce~ Lion of the latter in the 17 I water-fill mAchine The water used has 10 grains/gallon hardness and a pH of 7 to 7.5 prior to (about 9 to about 10.5 after) addition ofthe dt;~elgen~ and bleAching system.
The fabrics are laundered at 40C (104F) for a full cycle (40 min.) and rinsed at 21C (70F). The laundering method is repeated for 2,000 wash cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and pe,ro,--lal1ce.
EXAMPLE VI
A de~e-~,t;llL composition is prepared by a procedure id~nticAI to that of 0 Example V, with the single exception that an equivalent amount of benzoyloxybenzene sulfonate is substituted for the nonanoyl caprolactam. The laundering method of Example V is repeated for about 1200 cycles at which time the natural rubber parts ruptures.
EXAMPLE VII
A detergent composition is p-t:pa.ed by a procedure identical to that of Example V, with the single exception that an equivalent amount of (6-nonA~ idQcaproyl)-oxyl~e~ ,.e~.llfonate as prepared in Example m is s~bstit~lted for the nonanoyl caprolactam. The laundering method of Example V isrepeated for 2000 cycles without rupture of, or .~ignifiçAnt damage to, the natural rubber parts and with good enzyme stability and pe~rulll~ance~
EXAMPLE VIII
A detergent composition is prepared by a procedure idçnti~AI to that of F.Y~mple V, with the exceptions that 15% of a 1:1:1 mixture of benzoyl caprolactam, nonanoyl caprol~ .t~m and (6-n--n~ idocdployl)c,A~el~ene-s -IfonAte as p.~dred following Example m is substituted for the n onz~loyl caprolactam and the amount of sodium percarbonate is 30%. The laundering method of Example V is repeated for 2,000 cycles without rupture of, or signific~nt damage to, the natural rubber parts and with good enzyme stability and pelroll,lance.
EXAMPI,E IX
A detergent composition is pl~pal~d by a procedure identi~AI to that of Example IV, with the exceptions that 20% of a 1:1 mixture of benzoyl caprolactamand (6-nonAn~ ocaproyl)o~el~ l-es--lfonate as plepaled following Example m is substituted for the nonanoyl caprolactam, the amount of sodium percarbonate is 20%, and the amount of phosphate is 0%. The laundering method of Example IV is 3s repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and pCI rul ",ance.
EXAMPLE X

SUBSTITV~ SHE~T lRULE 26) ~1\ WO 94/28106 ~16 ~2 ~2 PCTIUS94/05372 A detergent composition is prel)aled by a procedure identical to that of Example V, with the single exception that an equivalent amount of a benzoxazin-type activator is substituted for the nonanoyl caprolactam. The laundering method of Example V is repeated for 2,000 cycles without rupture of, or signific~nt damage to, s the natural rubber parts and with good enzyme stability and pe~ru~mance.
EXAMPLE XI
A detergent composition is prepared by a procedure identical to that of Example V, with the exceptions that 10% of a 1:1 mixture of a benzoxa~ -type activator and tetraacetyl ethylene ~ min~ is substituted for the nonanoyl caprolactam 0 and the amount of sodium percarbonate is 25%. The laundering method of ExampleV is repeated for 2,000 cycles without rupture of, or significant damage to, thenatural rubber parts and with good enzyme stability and performance.
EXAMPLE XII
A laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and co"~plises the following:
Component Wei~ht %
C12 linear alkyl benzene sulfonate 30 Phosphate (as sodium tripolyphosphate) 7 Sodium carbonate 25 Sodium pyrophosphate 7 Coconut monoeth~nolamide 2 Zeolite A (0.1-10 micron) . 5 C~bu~y~ y~ lose 0.2 Polyacrylate (m.w. 1400) 0.2 (6-11ol~ 0r~ployl)o~ pJJlfonate 5 Sodium percarbonate 5 Bl-~ r, ~;lru~ne 0.2 Protease (as Protease C) 0.3 Lipase (as LIPOLASE) 0.3 CaSO4 MgSO4 Water 4 Filler* Balance to 100%
*Can be selected from convenient materials such as CaCO3, talc, clay, silicates, and 3s the like.
The d~telge..l laundry bars are processed in conventional soap or detergent bar making equipment as commonly used in the art. Testing is con-h1cted following SIJBST~T~TE SHEET (RULE 26~

the procedures and methods in Example V. The laundering method is repeated for 2,000 wash cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and pe. Çul ".ance.
EXAMPLE XIII
s A d~le~ge"L composition is prepal~d by a procedure identical to that of Example X~I, with the single exception that an equivalent amount of benzoyl caprolactam is substituted for the (6-nonana-l~idocaproyl)oxyben7enesl-1fonate. The laundering method of Example XII is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and 10 pe.r~,,ance.
EXAMPLE ~V
A detergent composition is prepared by a procedure identical to that of Example XII, with the single exception that an equivalent amount of nonanoyl caprolactam is substituted for the (6-non~n~midQcaproyl)oxyb~n7enesl11fonate. The laundering method of Example XlI is repeated for 2,000 cycles without rupture of, or .eignific~nt damage to, the natural rubber parts and with good enzyme stability and pe-rul-..ance.
EXAMPLE XV
A granular detergent composition is p.~ared comprising the following ingredients.
Component Wei~ht %
Anionic alkyl sulfate 7 Nonionic surfactant 5 Zeolite (0.1-10 micron) 10 2s Tri~otiillm citrate 2 SKS-6 silicate builder 10 Acrylate maleate polymer 4 Nonanoyl caprolactam 5 Sodium pelca.l,onate* 15 Sodium carbonate 5 Ethylç~led~ r~iCllcçin~te chelant (EDDS) 0.4 Suds supplessor 2 Protease (as Protease C) 0.5 Soil release agent 0.2 3s Minors, filler** and water Balance to 100%
*Average particle size of 400 to 1200 microns.
**Can be selected from convenient materials such as CaCO3, talc, clay, ~ilic~tes, and SIJBSTITIJTE SHEET (Rl ILE 26) ~ WO 94/28106 216 1 2 12 PCT/US94/05372 the like.
Aqueous crutcher mixes of heat and alkali stable components of the detergent composition are plepared and spray-dried, and the other ingredients are admixed so that they contain the ingredients tabulated at the levels shown.
Testing is cond-lcted following the procedures and methods in Example V.
The laundering method of Example V is epealed for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and p~lr~....al-ce.
EXAMPLE XVI
o A detergent composition is prepared by a procedure identical to that ofExample XV, with the single exception that an equivalent amount of benzoyl caprolactam is substituted for the nonanoyl caprolactam.
Testing is con~llcted following the procedures and methods in Example V.
The laund~ring method of Example V is repeated for 2,000 cycles without rupture of, or cignific~nt damage to, the natural rubber parts and with good enzyme stability and pe.r~ ance.
EXAMPLE XVII
A detergent composition is prepa-t;d by a procedure identical to that of Example XV, with the exceptions that 15%, by weight, of (¢nonana.ll,do-caproyl)oxybP~.7~-e~ lfonate is substitllted for the nonanoyl caprolactam and the amount of sodium percarbonate is 30%.
Testing is cond~lcted following the procedures and methods in Example V.
The l~l-n~lering method of Example V is lepe~ted for 2,000 cycles without rupture of, or s;~ c~ je to, the natural rubber parts and with good enzyme ~l~bilily and ~ r ll"al~ce.
EXAMPLE XVIII
A detergent composition is prel)aled by a procedure id~ntic~l to that of Example XV, with the exceptions that 15%, by weight, of a 1:1 mixture of (6-non~n~ dQcaproyl)oxyl,el~ e~.-lfonate and (6-dec~n~midocaproyl)oxybenzene-sulfonate activator is sukstitllted for the nonanoyl caprolactam and the amount of sodium p~ ;&,l,onale is 30%.
Testing is con-l~lcted following the procedures and methods in Example V.
The laundering method of Example V is repeated for 2,000 cycles without rupture of, or signific~nt damage to, the natural rubber parts and with good enzyme stability and pe-ro,-llance.
EXAMPLE XlX
A detergent colnposition is ple~)&led by a procedure identical to that of SUBSTITUTE SltEET (RULE 2~) WO 94128106 7~ PCT/US94/05372 ~1 Example XV, with the exceptions that 15%, by weight, of a 1:1 mixture of (6-oct~n~midocaproyl)oxyben7Pnçsl-lfonate and (6-dec~n~midocaproyl)oxybenzene-sulfonate activator is substituted for the nonanoyl caprolactam and the amount of sodium pelc~l,olldle is 30%.
S Testing is con~ cted following the procedures and methods in Example V.
The laundering method of Example V is repeated for 2,000 cycles without rupture of, or significant damage to, the natural rubber parts and with good enzyme stability and pe,ro""ance.
EXAMPLE XX
o A detergent composition is prepared by a procedure identical to that of Example XV, with the exceptions that 15%, by weight, of (6-oct~n~miclocaproyl)-oxybç~ -e,lllfonate is substituted for the nonanoyl caprolactam and the amount of sodium percarbonate is 30%.
Testing is con-lucted following the procedures and methods in Example V.
The laundering method of Example V is repeated for 2,000 cycles without rupture of, or signific~nt damage to, the natural rubber parts and with good enzyme stability and pe,rol-,lance.
EXAMPLE XXI
A detergent composition is prepaled by a procedure identical to that of 20 Example XV, with the exceptions that 15%, by weight, of (6-dec~ ".;~1ocaproyl)-o~yl,e~ -ç~.-lfonate activator is substituted for the nonanoyl caprolactam and the amount of sodium percarbonate is 30%.
Testing is co~lucted following the procedures and methods in F.Y~mple V.
The laundering method of Example V is ,~led for 2,000 cycles without rupture of,25 or significant damage to, the natural rubber parts and with good enzyme stability and pelfolll~allce.
Method of Processing the Bleach Activators The bleach activators may be processed with a range of organic and inorganic substances to achieve a rapid dispersion in the blç~çhing liquor and to insure good 30 stability in the deLel~,enL composition. The bleach a~iliv~ol~ are plerelably employed in particulate form.
An example of p~c;r~ d caprolactam bleach activator particles is an agglomerate of about 65%, by weight, benzoyl caprolactam; about 7% of a builder,such as ~ minillm silicate; about 15% sodium carbonate; about 9% dispersant, such 3~ as a polyacrylate polymer; and about 4% of a solubilizing agent, such as a linear alkyl sulfonate. Another example of a p,erell~d caprolactam bleach activator particle is an agglG",e,~le of about 80% to about 85%, by weight, benzoyl caprolactam and about SU~ST~TUTE SHEET (RULE 26J

Wo 94/28106 ~ 212 PcTluss4lo5372 15% to about 20% of a binder, such as tallow alcohol ethoxylate, preferably TAE25.
An FY~mple of a plefe,led amido-derived bleach activator particle comprises a 1: 1: 1 mixture of (6-oct~n~midocaproyl)oxybçn7enes..lfonate, (6-dec~ ...idocaproyl)-oAybel-,Fl-F~.llfonate~ and citric acid powder. The mixture is s ;,,~ ly mixed in a food mixer for 5-10 min~tes To the r~sult~nt mixture is added tallow alcohol ethoxylate (TAE25) nonionic surfactant at 50 C until granules are formed. Typically su~cçscful granulations are achieved with a ratio of bleach activator/citric acid solid mixtures:nonionic binding agent of 3.5:1. The resultant granules, ellipsodial and spherical in shape, are white and free flowing.
A typical particle composition is about 40% to about 60%, preferably about 55%, by weight, of the bleach activator or mixture of bleach activators; about 20% to about 40%, preferably about 25%, by weight, of citric acid; and about 15% to about 30%, preferably about 20%, by weight, TAE25 binding agent. Alternatively, a 2:1 mixture of (6-dec~ docaproyl)oxyb~ F~-F,~.lfonate and citric acid powder may be used. In this case, the composition on the granule is 55% bleach activator, 25%
citric acid, and 20% TAE25 binding agent. Other prcr~lled organic binding agentsinclude anionic surf~ct~nt~ (C12 linear alkyl bc;l~enc sulfonates), polyethyleneglycols, and TAE50.
Another example of a ~ re~led amido-derived bleach activator particle comprises a 1:1:1 mixture of (6-oct~n~midocaproyl)oxylJel~el,esulfonate, (6-decan-amidocaproyl)o,~il,r..,-.-e~lfon~tF, and sodium hydrogen sulfate. To the mixture is added 20% by weight of an anionic surfactant (alkyl sulfate is particularly perferred).
The ~."~)one.~ls are mixed into a paste with water, typically 30-50% by weight of water being added, and introduced into an air flow such that dr~ tc are formed.
2s This t~l-;n~ e is COm~llOI~ known as spray drying. This may be acli_.cd using, for CA~UIIPI~ a Nyro alur..;~el-, or a spray gun. Hot air (typically 150-300 degree Celisius) is blasted u~ alds through a column. The rw..lting particles formed are collected at the bottom of the column and classified into desired size.
A typical particle composition is about 40-60%, preferably about 55%, by 30 weight of the bleach activator or nllA~ e of activalo.~, about 20~0%, preferably about 25%, of sodium hydrogen sulfate, and about 15-25%, p~ir~;~ably about 20%, of anionic surfactant. Alternatively, a 2: 1 mixture of (6-dec~n~midocaproyl)oA~F~ e~ fonate and sodium hydrogen sulfate may be used.
Citric acid or boric acid may also be used in place of sodium hydrogen sulfate in the 3s above examples.

SU~STIT~JTE SH~ET ~RULF 26~

W O 94128106 2 ~ ~ ~ 2 ~ 2 PCTrUS94/05372 The particle size of the resulting granules may be varied according to the desired pe~ "ance/stability. Fine particles (<250 um) show improved solubility;
though coarse particles (>1180 um) are more stable in high ten~pe~aLLIres/moist envilolll.le..l~. A typical, prere..ed particle size range is 250-1180 um; particles ~i col~ ng to this speçifiç~tion show excellent stability and solubility.

SU~STlTl~TE ~EET (RIJLE 26)

Claims (21)

WHAT IS CLAIMED IS:

1. A detergent composition comprising an effective amount of one or more types of enzymes and a bleaching system comprising at least 0.1% by weight of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor and at least 0.1% by weight of one or more bleach activators, wherein said bleach activators are members selected from the group consisting of a) a bleach activator of the general formula:

, or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group;
b) a benzoxazin-type bleach activator of the formula:

wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein m R6 is H or an alkyl group and carbonyl functions;
c) a N-acyl caprolactam bleach activator of the formula:

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from1 to 12 carbons; and d) mixtures of a), b) and c).

2. A composition according to Claim 1 wherein said enzymes comprise at least 0 001%, by weight of said detergent composition, and are selected from the group consisting of proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof.

3. A composition according to Claim 2 wherein said enzyme is lipase derived from the fungus Humicola lanuginosa or a modified bacterial serine protease derived from Bacillus subtilis, Bacillus lentus, or Bacillus licheniformis.

4. A composition according to Claim 2 wherein said bleach activator is selected from the group consisting of a) a bleach activator of the formula:

, or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group;
b) a N-acyl caprolactam bleach activator of the formula:

wherein R6 is H or an allyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons; and c) mixtures of a) and b);
and said enzyme is selected from the group consisting of SAVINASE, Protease C, and mixtures thereof.

5. A composition according to Claim 1 or Claim 4 wherein said bleach activator is selected from the group consisting of benzoyl caprolactam, nonanoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, decanoyl caprolactam,undecenoyl caprolactam, (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxyben-zenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof; said enzyme is Protease C; and said peroxygen bleaching compound is selected from the group consisting of sodium perborate monohydrate, sodium perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, sodium peroxide and mixtures thereof.

6. A composition according to Claim 1 or Claim 4 wherein the bleach activators are in particulate form, preferably spray dried particles.

7. A composition according to Claim 1 or Claim 4 wherein the molar ratio of hydrogen peroxide to bleach activator is greater than approximately 1Ø

8. A composition according to Claim 1 wherein R1 is an alkyl group containing from 6 to 12, preferably from 7 to 10, carbon atoms; R2 contains from 1 to 8, preferably from 4 to 5, carbon atoms; R5 is H or methyl; and L is selected from the group consisting of:

, , and , , , , , , , , , and , and mixtures thereof, wherein R1 is as defined in Claim 1, R3 is an alkyl chain containing from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizinggroup.

9. A composition according to Claim 8 wherein L is selected from the group consisting of:

, , and wherein R3 is an alkyl chain containing from 1 to 8 carbon atoms, Y is -SO3-M+ or -CO2-M+ wherein M is sodium or potassium.

10. A composition according to Claim 1 wherein said benzoxazin-type bleach activator has the formula:

11. A composition according to Claim 1 further comprising from 5% to 80%, by weight, of a detersive surfactant; from 5% to 80%, by weight, of a detersive builder;
and from 0% to 20%, by weight, of conventional detersive adjuncts.

12. A method for cleaning fabrics in an automatic washing machine having parts made of natural rubber which is susceptible to oxidative degradation, said method comprising agitating said fabrics in said machine in an aqueous liquor comprising a detergent composition according to Claim 1, such that said natural rubber parts of said machine are substantially undamaged by the detergent composition.

13. A method according to Claim 12 wherein said bleaching system comprises at least 0.1%, by weight, of one or more bleach activators, wherein said bleach activators are selected from the group consisting of:
a) a bleach activator of the general formula:

, or mixtures thereof,wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group;
b) a benzoxazin-type bleach activator of the formula:

wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5 may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkylamino, -COOR6, wherein R6 is H or an alkyl group and carbonyl functions;
c) a N-acyl caprolactam bleach activator of the formula:

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbons; and d) mixtures of a), b), and c).

13. A method according to Claim 12 wherein said bleaching system further comprises at least 0.1%, by weight, of a peroxygen bleaching compound capable ofyielding hydrogen peroxide in an aqueous liquor; wherein said peroxygen bleaching compound is selected from the group consisting of sodium perborate, monohydrate sodium perborate tetrahydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium percarbonate, sodium peroxide and mixtures thereof.

14. A method according to Claim 13 wherein said enzymes comprise at least 0.001%, by weight of detergent composition, of said detergent composition and are selected from the group consisting of proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof.

15. A method according to Claim 14 wherein said enzyme is lipase derived from the fungus Humicola lanuginosa or wherein said enzyme is a modified bacterial serine protease derived from Bacillus subtilis, Bacillus lentus, or Bacillus licheniformis.

16. A method according to Claim 15 wherein said bleach activator is selected from the group consisting of:
a) a bleach activator of the formula:

, or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms, and L is a leaving group;
b) a N-acyl caprolactam bleach activator of the formula:

wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbons; and c) mixtures of a) and b);
and said enzyme is selected from the group consisting of SAVINASE, Protease C, and mixtures thereof.

17. A method according to Claim 16 wherein said bleach activator is selected from the group consisting of benzoyl caprolactam, nonanoyl caprolactam (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy-benzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mix-tures thereof; and wherein said enzyme is Protease C.

18. A detergent composition comprising:
a) at least 0.001% of one or more types of enzymes selected from the group consisting of proteases, amylases, lipases, cellulases, and peroxidases and mixtures thereof; and b) a bleaching system comprising at least 0.1% by weight of a substantially insoluble organic peroxyacid having the general formula:

, wherein R1 is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms.

19. A composition according to Claim 18 wherein said enzyme is lipase derived from the fungus Humicola lanuginosa or wherein said enzyme is a modified bacterial serine protease derived from Bacillus subtilis, Bacillus lentus, or Bacillus licheniformis.

20. A composition according to Claim 18 further comprising from 5% to 80%, by weight, of a detersive surfactant, from 5% to 80%, by weight, of a detersive builder and from 0% to 20%, by weight, of conventional detersive adjuncts.

21. A method for providing enhanced dingy cleanup, said method comprising agitating said fabrics in said machine in an aqueous liquor comprising conventional detergent ingredients according to Claim 18.