CA2161211C - Bleaching compositions comprising peroxyacid activators having amide moieties - Google Patents

Abstract

The present invention relates to a method of cleaning fabrics in washing machines which have parts made of natural rubber using laundry detergents comprising amido-derived bleaching activators and a source of hydrogen peroxide such that said natural lubber parts of said machines are substantially undamaged by products of the perhydrolysis reaction between the activator and hydrogen peroxide.

Description

~i6~z~~
BLEACHING COMPOS1~TIONS COMPRISING
PEROXYACm ACTIVATORS HAVING AMIDE MOIETIES
FIELD OF THE i)NVENTION
The present invention relates t~p laundry detergents with activated bleaching systems.
BACKGROUND OF '~''1~ INVENTION
It has long been known that peroprygen bleaches are effective for stain and/or soil removal from fabrics, but that such bleaches are temperature dependent. At a wash liquor temperatuire of 60°C) peroxygen bleaches are only partially effective As the wash liquor temperature is lowered below 60°C, peroxygen bleaches become relatilvely ineffective. As a consequence) there has been a substantial amount of industrial research to develop bleaching =0 rystems which contain an activator that readers peroxygen bleaches effective at wash liquor temperatures below 60°C.
Numerous substances have been d~ixlosed in the art as effective bleach activators. One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TA>:D provides effective hydrophilic cleaning especially on beverage :5 stains) but has limited performance on idingy) yellow stains such as those resulting from body oils Another tyke of activator) such as nonanoyl oxybenzenesulfonate (HOBS) and other ~etivators which generally comprise long chain alkyl moieties, is hydrophobic in nature and provides excellent performance on dingy stains However, 'many of the hydrophobic activators 30 developed thus far can promote damage tip natural rubber parts used in certain washing machines Because of these negative effects on washing machine parts) the selection of such detergent-addled bleaching systems has long bren limited. This is especially true for Eurolpean detergentJbleaches, since many washing machines manufactured in Europt~ have been equipped with key parts) 35 such as sump hoses and motor gaskets)'' made of natural rubber. A need_ therefore) exists for a bleaching system iwhich provides dingy soil clean up without substantially damaging the n~ktural rubber parts found in washing machines.
It has now been determined that in conventional bleaching systems) typically comprising a hydrophobic bleach activator and a source of hydrogen peroxide, the activator undergoes perhydrolysis to form a peroxyacid bleaching agent. A by-product of the perhydiolysis reaction between such bleach activators and hydrogen peroxide is a Idiacylperoxide (DAP) species. It has now further beat discovaod that thpe DAP's derived from hydrophobic bleaching activators tend to be insoluble) poorly dispersible) oily materials 0 which form a residue which can deposit on the natural rubber machine parts that are exposed to the wash liquor. Ttue oily DAP residue can form a film on the natural rubber parts and promote free radical and peroxide damage to the rubber) which eventually leads to failure; of the parts. This is particularly true of rubber parts which have prolonged exposure to the wash liquor) such as sump hoses.
By the present invention, it has now been discovered that the class of hydrophobic bleach activators derived from amido acids forms hydrophobic amido peracids upon perhydrolysis without the production of harmful) oily DAP's. Without limiting the invention i herein, it is believed that the DAP's =o produced by the perhydrolysis reactioln of the amido acid-derived bleach activators are insoluble crystalline soiid~. Such solid DAP's do not form a coating film. Accordingly, the natural nrbber machine parts are not exposed to the DAP's for extended periods of time artd remain substantially undamaged by the bleaching system of the present invention.
The present invention thus soNves the long-standing need for an eH'ective hydrophobic bleaching system .which does not promote free radical and peroxide damage to natural rubber parts in washing machines. The invention provides a method of cleaning fabrics with a bleaching system in washing machines which have parts mode of natural rubber such that the natural rubber is substantially undamagedby the bleaching system.
3o BACKGROLiND ART , U.S. Patent 4,634,551) Burns et ~1) issued January 6) 1987, discloses amido peroxyacid bleaching compounds and their precursors of the type , employed in the present invention. See also, U.S. Patent 4,852,989, Burns et al, issued August 1, 1989, and U.S. Paterwt 4,966,723) Hodge et al, issued Oct.
30) 1990.

WO 94/28104 ~ ' PCT/US94/05370 SUMMARY OF TlE-iE INVENTION
The present invention relates ~to a method for cleaning fabrics in automatic washing machines having patrts made of natural rubber which is susceptible to oxidative degradation. The method comprises agitating fabrics in said washing machine in an aqueous jliquor comprising a bleaching system comprising a bleach activator which reacts with a source of peroxide its said aqueous liquor to yield a peroxyac~d without the formation of oily diarylperoxide (DAP) such that said natural rubber parts are substantially undamaged by the by-products of said reaction.
The amido-derived peroxyacids ;generated by the reaction are of the general formulas:

R~-C-N-RZ-C-OOH , R~--N-C-R2-C-OOH
Rs Rs wherein R 1 is an alkyl) aryl, or alkaryl grpup containing from about 1 to about 14 carbon atoms) R2 is an alkylene) arylene or alkarylene group containing from about I to about 14 carbon atoms, alnd RS is H or an alkyl, aryl, or alkaryl goup containing from about 1 to about 10 carbon atoms.
2o The bleaching rystem of said method comprises:
a) at least about 0.1~/0, preferably from about 1% to about 75%) by weight) of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor; and b) at least about 0.1 ~/., preferabl;w from about 0.1 % to about 50%, by weight) of a bleach activator selected fronp the group consisting of:
z5 i) O O , '- 0 2-O
R'--C-N-RZ-C-L, R N-C-R C-L
RS Rs 30 or mixtures thereof, wherein R 1' is an alkyl) aryl) or alkaryl group containing from about 1 to about 14 carton atoms) RZ is an alkylene, arylene or alkarylene group containing from abou~l 1 to about 14 carbon atoms) RS is H
or an alkyl) aryl, or alkaryl goup containpng from about 1 to about 10 carbon atoms, and L is a leaving group; '

2~1fi1~1~
ii) R3 ~O
I
~ , C -R~

Rs wherein RI is H) alkyl) alkaryl) aryl, aralkyl) and wherein R2, R3, R4, and RS may be the same or different substituents selected from H, halogen, 1 o alkyl) alkenyl, aryl, hydroxyl) alkoxyl) amino) alkylamino) COOR6 (wherein is H or an alkyl group) and carbonyl functions; and iii) mixtures of i) and ii).
Preferably the molar ratio of hydrogen peroxide yielded by a) to bleach activator b) is greater than about 1Ø Most preferably) the molar ratio of hydrogen peroxide yielded by a) to bleach activator b) is at least about 1.5.
The invention also encompasses laundry compositions in granular) paste) liquid) or bar form which comprise the aforesaid bleaching system together with detersive ingredients which are present in the composition at the levels indicated hereinafter.
Preferred bleach activators of type b)i) are those wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 contains from about 1 to about 8 carbon atoms, and RS is H or methyl. Particularly preferred bleach activators of type b)i) are those of the above general formulas wherein, R 1 is an alkyl goup containing from about 7 to about 10 carbon atoms and R2 2 5 contains from about 4 to 5 carbon atoms.
Preferred bleach activators of type b)ii) are those wherein R2, R3, R4) and RS are H and R 1 is a phenyl group.
The peroxygen bleaching compound can be any peroxide source and is preferably a member selected from the group consisting of sodium perborate monoh'ydrate) sodium perborate tetrahydrate, sodium percarbonate, sodium pyrophosphate peroxyhydrate) urea peroxyhydrate) sodium peroxide and mixtures thereof. Highly preferred peroxygen bleaching compounds are selected from the group consisting of sodium perborate monohydrate) sodium perborate tetrahydrate, sodium percarbonate and mixtures thereof. The most highly preferred peroxygen bleaching compound is sodium percarbonate.

n ..

The bleach activators herein can also be used in combination with rubber-safe, hydrophilic activators such as TAED, typically at weight ratios of amido-derived activators:TAED in the range of 1:5 to 5:1, preferably about 1:1. Another important class of rubber-safe, hydrophilic activators comprise the N-acyl caprolactam activators wherein the acyl moiety has the formula Rl-CO- wherein Rl contains 6 or less carbon atoms. Highly preferred hydrophilic caprolactam activators include formyl caprolactam, acetyl caprolactam, and benzoyl caprolactam.
The method of cleaning fabrics comprises agitating fabrics in said washing machine in an aqueous liquor comprising a detergent composition which comprises at least about 300 ppm of conventional detergent ingredients, at least about 25 ppm of the bleaching compound and at least about 25 ppm of a bleach activator.
Preferably, the liquor comprises from about 900 ppm to about 20,000 ppm of conventional detergent ingredients, from about 100 ppm to about 25,000 ppm of the bleaching compound and from about 100 ppm to about 2,500 ppm of a bleach activator. The method can be successfully carried out at temperatures below about 60°C but, of course, is quite effective and is still safe to rubber parts at laundry temperatures up to the boil.
The conventional detergent ingredients employed in fully formulated detergent compositions provided herein can comprise from about 1 % to about 99.8%, preferably from about 5% to about 80%, of a detersive surfactant. Optionally, detergent compositions can comprise from about 5% to about 80% of a detersive builder.
Other optional detergent ingredients are also encompassed by the fully-formulated detergentJbleach compositions provided by this invention.
All percentages, ratios, and proportions are by weight, unless otherwise specified.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to a method for cleaning fabrics in automatic washing machines having parts made of natural rubber which is susceptible to oxidative degradation. The bleaching system used in this invention is safe to natural rubber machine parts and to other natural rubber articles which are exposed to the bleaching system, including fabrics containing natural rubber and natural rubber elastic materials. The bleaching system employed in the present invention provides effective and efficient surface bleaching of fabrics which thereby removes stains and/or soils, including "dingy" soils, from the ~I~f~~l fabrics. Dingy soils are soils that buildup on fabrics after numerous cycles of usage and washing and, thus) eventuallyi cause white fabrics to have a gray or yellow tint. These soils tend to be a blend of particulate and greasy materials.
The removal of this type of soil is some~Gimes referred to as "dingy fabric clean up'.
The bleaching systems and ';activators herein afford additional advantages in that, unexpextexlly) they ate safer to fabrics and cause less color damage than other activators when uiaed in the manner provided by this invention.
t o The bleaching mechanism and, in particular) the surface bleaching mechanism are not completely understoiod. However) it is generally believed that the bleach activator undergoes n~~cleophilic attack by a perhydroxide anion, which is generated from the hydrogen peroxide evolved by the peroxygen bleach) to form a peroxycarb~I~xylic acid. This reaction is commonly referred to as perhydrolysis.
It is also believed, that the blea~th activators within the invention can render peroxygen bleaches more efficient even at wash liquor temperatures wherein bleach activators are not neces;kary to activate the bleach, i.e., above about 60oC. Therefore) with bleach systems of the invention, less peroxygen bleach is requirexi to get the same level ~pf surface bleaching performance as is obtained with the peroxygen bleach alone.
The Bleach Activator The hydrophobic bleach activat~prs employed with this invention are amide substituted compounds of the genyral formulas:
:s RFC-N-R~-C-L
I , R N C-R C-L
Rs Rs or mixtures thereof) wherein R 1, R2, and RS are as defined hereinabove and L
~n 'essentially any suitable leaving grc>up. A leaving group is any group that is displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction) results in the foilmation of the peroxycarboxylic acid.
Generally, for a group to be a suitable having group it must exert an electron attracting effect. It should also form a stiable entity so that the rate of the back ~161~~ :~

~1 reaction is negligible. This facilitates the nucleophilic attack by the perhy-droxide anion.
The L group must be sufficienr<ly 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 difficullt to stabilize for use in a bleaching composition. These characteristics are ;;generally paralleled by the pKa of the conjugate acid of the leaving group, altluough exceptions to this convention are known. Ordinarily) leaving groups that exhibit such behavior are those in which their conjugate aad has a pKa in yhe range of from about 4 to about 13) o preferably from about 6 to about 1 l and'; most preferably from about 8 to about Preferred bleach activators are ; those of the above general formula wherein Rl) RZ and RS are as defined! for the peroxyacid and L is selected from the group consisting of Y R~ R3Y
-Y , and O O
-N- II -R~ II
C -N N -N-C -C H-R, Ra ' ~ ~ R3 Y , I
Y
Y
2 5 -p-C H=C -C H=C Hz -O-i~C H=C -C H=C H2 O C ~ Y 0 ,~ ~--C, -O-C-R' -N~C~NFI~ , 'N~C/N~
II II
O O

3 R O Y
-O-C=C HR, ( and -N-S-C H-R4

4 PCT/US94/05370 yl~ X211 and mixtures thereof, wherein R 1 is an alkyl) aryl, or alkaryl group containing from about 1 to about 14 carbon atoms) R3 is an alkyl chain containing from 1 to about 8 carbon atoms, R4 is H or R3) and Y is H or a solubilizing group.
The preferred solubiliung groups are -S03-M+) -CO -M+,-S04 -M+, -N+(R3)47~ and O<-N(R3)3 and most preferably -S03-M~ and -C02-M+
wherein R3 is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a ration 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 ration, with sodium and potassium t o being most preferred) and X is a halide, hydroxide methylsulfate or acetate anion. It should be noted that bleach activators with a leaving group that does not contain a solubiliz~ng groups should be well disperxd in the bleaching.
solution in order to assist in their dissolution.
Preferred bleach activators are thox of the above general formula wherein L is xlected from the group consisting of:

-O ~ , ~ Y , and -O
wherein R3 is as defined above and Y is -S03-M+ or -C02-M+ wherein M
is as defined above.
Another important class of bleach activators which provide organic peracids as described herein ring-opens as a consequence of., the nucleophilic attack on the carbonyl carbon of the cyclic ring by the perhydroxide anion.
This ring-opening reaction involves attack at the ring carbonyl by hydrogen 2 5 peroxide or its anion Examples of ring-opening bleach activators can be found 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 benzoxazin-type) having the formula:
O
C
O
of ,~~-R, N
including the substituted benaoxaz~ns of the type WO 94/28104 ~ i PCTlUS94/05370 .o o '-~N4C
wherein R 1 is H, alkyl) alkaryl, aryl, aral~Cyl, and wherein R2) R3) R4, and RS
may be the same or different substituqnts selected from H) halogen, alkyl, alkenyl, aryl) hydroxyl) alkoxyl) amino, a~kyl-amino) COOR6 (wherein R6 is H
0 or an alkyl group) and carbonyl functions A preferred activator of the benzc~xavn-type is:
II
C
I;
is o N
The bleach activators employed herein will comprise at least about 0. I %, preferably from about 0.1 % to about 50%, more preferably from about 1% to about 30%, most preferably from out 3% to about 25%) by weight of 20 the bleaching system or detergent composlNnon.
When the activators are used, op>~imum surface bleaching performance is obtained with washing solutions whereiln the pH of such solution is between about 8.5 and 10.5 and preferably betwejen 9.5 and 10.5 in order to facilitate the perhydrolysis reaction. Such pH can b~ obtained with substances commonly 25 known as buffering agents) which are olptional components of the bleaching systems herein.
The Peroxygen Bleaching Compound The bleaching systems, wherein thie bleach activator is used, also have as an essential component a peroxygen bileach capable of releasing hydrogen 30 peroxide in aqueous solution.
The peroxygen bleaching systems; useful herein are those capable of yielding hydrogen peroxide in an aqueousE liquor. These compounds are well known in the an and include hydrogen perioxide and the alkali metal peroxides) organic peroxide bleaching compounds such as urea peroxide, and inorganic 35 persalt bleaching compounds, such its the alkali metal perborates) WO 94/28104 f.' ~ ~ ~2 ~ PCT/US94/05370 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, commercially available in the foam of mono-) tri-, and tetra-hydrate, sodium

5 percarbonate) sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium pacarbonate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such t 0 rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhanced surface bleaching performance.
Highly preferred percarbonate can be in uncoated or coated form. The average particle siu of uncoated percarbonate ranges from about 400 to about 1200 microns) most preferably from about 400 to about 600 microns. If coated percarbonate is used, the preferred coating materials include mixtures of carbonate and sulphate, silicate) borosilicate) or fatty carboxylic acids.
The peroxygen bleaching compound will comprise at least about 0. I %) preferably from about 1% to about 75%, more preferably from about 3% to about 40%, most preferably from about 3% to about 25%, by weight of the 10 bleaching rystem or detergent composition.
The weight ratio of bleach activator to peroxygen bleaching compound in the bleaching system ranges form about 2:1 to about 1:5. In preferred embodiments) the ratio ranges from about 1:1 to about I :3.
The bleach activator/bleaching compound rystems herein are uxful pcr 2 5 x as bleaches. However, such bleaching rystems are especially useful in compositions which can comprix various detersive adjuncts such as sur factants, builders, enzymes, and the like as disclosed hereinafter.
petersive Surfactant The amount of detersive surfactant included in the fully-formulated 30 detergent compositions afforded by the present invention can vary from about 1% to about 99.8% by weight of detergent composition depending upon the particular surfactants used and the effects desired. Preferably) the detersive surfactants comprise from about 5% to about 80% by weight of the composition.
35 The detersive surfactant can be nonionic, anionic) ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also be used.

WO 94/28104 ~~ ~ ~ ~~ ~ ~ PCT/US94/05370 Preferred detergent compositions corr~prise anionic detersive surfactants or mixtures of anionic surfactants with ;other surfactants, especially nonionic surfactants.
Nonlimiting exaJnples of suil~factants useful herein include the conventional C 11-C 18 alkyl benzene slulfonates and primary) secondary, and random alkyl sulfates) the C 1 ~-C 18 all~yl aJkoxy sulfates, the C 10-C 18 alkyl polyglycosides and their correspondiyg sulfated polyglycosides) C 12-C 18 alpha-sulfonated fatty acid esters) C 12-'C 18 alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethpxylpropoxy), C 12-C 18 betaines and sulfobetaines ("sultaines"), C 1 p-C 18 amine oxides) and the like. Other conven-tional useful surfactants are listed in sta.n~dard texts.
One particular class of adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty ajcid amides of the formula:
i5 2,;,0 R
(1) R vC-N-Z
wherein: R 1 is H, C 1-Cg hydrocart~yl) ;~-hydroxyethyl, 2-hydroxypropyl) or a mixture thereof) preferably C 1-C4 alkyl,! more preferably C 1 or C2 alkyl) most preferably C 1 alkyl (i.e., methyl); and jR2 is a CS-C32 hydrocarbyl moiety) preferably straight chain C~-C I 9 alkyl ~, or alkenyl) more preferably straight chain C9-C I ~ alkyl or aJkenyl) most pref~Crably straight chain C 11-C 19 alkyl or aJkenyl, or mixture thereof; and Z is a pa~yhydroxyhydrocarbyl 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 rj~ducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived f~om a reducing sugar in a reductive amination reaction; more preferably Z is~ a glycityl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose) galactose) mannose) and xyiose) a well as glyceraldehyde. As nor materials) high dextrose corn syrup, high fructose corn syrup, and high maJtosle corn syrup can be utilized as well as the individual sugars listed above. These; corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z', preferably will be selected from the group consisting of -CH2-(CHOH)n-C~H20H) -CH(CH20H)-(CHOH)n-1--CH20H, -CH2-(CHOH)2(CHOR')(CHI~H)-CH20H) where n is an integer from 1 to 5, inclusive) and R' is H or a cyclic mono- or poly- saccharide, and zml~~~

alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4 particularly -CH2-(CHOH)4-CH20H.
In Formula (I), R1 can be) for example) N-methyl, N-ethyl, N-propyl) N-isopropyl) N-butyl) N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
For highest sudsing, R I is preferably methyl or hydroxyalkyl. If lower sudsing is desired) R1 is preferably 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) cocamide) stearamide, oleamide) Isuramide) myristamide, capricamide, palmitamide) tallowamide) etc.
l0 ~sive Builders Optional detergent ingredients employed in the present invention contain inorganic 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 detergent compositions.
Inorganic detersive 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 sesquicartionates)) sulphates) and aluminosilicates. However) 10 non-phosphate builders are required in some locales.
Examples of silicate builders are the alkali metal silicates) particularly those having a Si02:Na20 ratio in the range 1.6:I 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, available from Hoechst under the trademark'SKS'; SKS-b is an especially preferred layered silicate builder.
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 detergents can be in the range of 450-850 g/I 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 l5) 1973.
Aluminosilicate builders are especially useful in the present invention.
Preferred aluminosilicates are zeolite builders which have the formula:
NaZI(A102)Z (Si02)y)'xH20 ~~s~ ~r~
WO 94/28104 ~ PCT/US94/05370 wherein z and y are integers of at leas~l 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 l5.to about 264.
Useful aluminosilicate ion extchange materials are commercially available. These aluminosiiicates can b~~ crystalline or amorphous in structure and can be naturally-occurring alurtuinosilicates or synthetically derived.
Methods for producing aluminosilicate iion exchange materials are disclosed in U.S. Patent 3,985,669) Krummel) et all) issued October 12, 1976) and U.S.
Patent 4,605,509) Corkill) et al) issued Aug. 12, 1986. Preferred synthetic crystalline aluminosilicate ion exchanger materials useful herein are available t o under the designations Zeolite A) Zeolite P (B), (including those disclosed in EPO 384,070)) and Zeolite X. Prefer~ly, the aluminosilicate has a particle size of about 0.1-10 microns in diameter;
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 polycarbo;irylates) including oxydisuccinate) as disclosed in Berg) U.S. Patent 3) 128,287 issued April 7) 1964) and Lamberti et al) U.S. Patent 3,635,830) issued lanu~ry 18, 1972. See also "TMSrfDS"
builders of U.S. Patent 4,663,071) issued to Bush et al) on May 5) 1987.
Other useful detersive builders include the ether hydroxypolycar boxylates, copolymers of malefic anhydride with ethylene or vinyl methyl ether) l ) 3) 5-trihydroxy beruene-2) 4, 6-trisulphonic acid) and carboxymethyl oxysuccinic acid, the vuious alksli ~ metal, ammonium and substituted ammonium salts of polyscetic acids ~ sucph as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as pdlycartioxylates such as mellitic acid) succinic acid) oxydisuccinic acid, polymjlleic acid) benzene 1,3,5-tticarboxylic acid) carboxymethyloxysuccinic acid) ands soluble salts thereof.
Citrate builders, a g., citric acid jand soluble salts thereof (particularly sodium salt), are preferred polycarboxyl~ate builders that can also be used in granular compositions, especially in co~Inbination with zeolite and/or layered 3o silicate builders.
Also suitable in the detergent conhpositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanodio~Ittes 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 the formulation of bars used for hand-laundering operations) the various alkali metal phosphates such as the well-known sodium WO 94/28104 a PCT/US94/05370 ~ 161 ~ ~. ~-tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-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 used.
Optional Detersive Ad,'ui nets As a preferred embodiment) the conventional detergent ingredients employed herein can be selected from typical detergent composition components such as detersive surfactants and detersive builders. Optionally) the detergent ingedients can include one or more other detersive adjuncts or other materials for assisting or enhancing cleaning performance, treatment of the wbstrate to be cleaned, or to modify the aesthetics of the detergent composition. Usual detersive adjuncts of detergent compositions include the.
ingedients set forth in U.S. Pat. No. 3,936,537) Baskerville et al. Adjuncts which can also be included in detergent compositions employed in the present invention, in their conventional art-established levels for use (generally from 0% to about 20°/. of the detergent ingedients) preferably from about 0.5% to about 10%), include enzymes) especially proteases, lipases) and cellulases, color speckles, wds boosters) wds suppressors) antitarnish and/or anticorrosion agents, soil-wspending agents, soil release agents) dyes) fillers, optical brighteners, germicides, alkalinity sources) hydrotropes) antioxidants) enzyme stabiliang agents) perfumes) solvents) solubilizing agents) clay soil removaUanti-redeposition agents) polymeric dispersing agents,_processing aids) fabric softening components, static control agents, etc.
Bleach systems optionally, but preferably) will also comprise a chelant which not only enhances bleach stability by scavenging heavy metal ions which tend to decompose bleaches, but also assists in the removal of polyphenolic stains such as tea stains, and the like. Various chelants, including the amino phosphonates) available as DEQUEST from Monsanto, the nitrilotriacetates, the hydroxyethyl-ethylenediamine triacetates, and the like) are known for such use. Preferred biodegradable) non-phosphorus chelants include ethylene-diamine diwccinate ("EDDS"; set U.S. Patent 4,704,233) Hartman and Perkins)) ethylenediamine-N,N-diglutamate (EDDG) and 2-hydroxypro-pylenediamine-N,N-diwccinate (I~DDS) compounds. Such chelants can be used in their alkali or alkaline earth metal salts) typically at levels from about 0. I % to about 10°/, of the present compositions.

WO 94/28104 ~ .~ ~ ~ ~ I 1'CT/US94/05370 Optionally, the detergent compositions employed herein can comprise, in addition to the bleaching system of that present invention) one or more other conventional bleaching agents) activator.i, or stabilizers which do not react with or otherwise harm natural nrbber. In general) the formulator will ensure that the bleach compounds used are compittible with the detergent formulation.
Conventional tesu) such as tests of bleach activity on storage in the presence of the separate or fully-formulated ingredients, can be used for this purpose.
Specific examples of optional blekch activators for incorporation in this invention include tetraacetyl ethylerpe diamine (TAED) and N-acyl t o uprolactams. Highly preferred N-t<cyl caprolactams include benzoyl caprolactam and those wherein the acy~ moieties have the formula R I -CO-wherein R I is H or an alkyl, aryl) arkaryll) or alkoxyaryl group containing from I to 12 carbon atoms, preferably 1 to 6 Gltrbon atoms.
Such bleaching compounds and agents can be optionally included in detergent compositions in their conveytional 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 compositiions such as those typically found in granular detergents or laundry bars. U.~G. Patent 3) 178,370, Okenfuss) issued April 13) 1965, describes laundry detergent bars and processes for making them. Philippine Patent 13,778, Andersen) issued Sept. 23, 1980, describes synthetic detergent laundry bars. Methods for making laundry detergent bars by various extrusion methods are well kndwn in the art.
The following examples are given to further illustrate the present invention) but are not intended to be limitijng thereof.
FX~MP E I
Synthesis of (6-Nonanamidocaproyl)oxyb~tnzenesulfonate (NACA-OBS).

6-Nonanamidocaproic Acid (NAC'~A,) - The reaction is carried out in a 12L 3-necked flask equipped with a '~ thermometer) addition funnel and mechanical stirrer. To a solution madet from 2128 (5.3 moles) of sodium hydroxide and 6L of water (cooled to rocarr temperature) is added 694.38 (5.3 moles) of 6-aminocaproic acid. This mixture is cooled to 10°C and a solution of 694.38 (5.~ moles) of nonanoyl chloride in I L of ether is added in a slow stream (about 2.5 hours) keeping the temperature at 10-15°C. During the addition, and subsequently until acidification) the reaction is maintained at pH
11-12 by periodic addition of 50% NaOH, ARer the addition is complete, the WO 94/28104 ~) PCT/US94/05370 reaction is stirred for another 2 hours at 10°C and allowed to come to room temperature before acidification to pH 1 with conc. HCI. The precipitated product is vacuum filtered) the filter cake is washed twice with 8L portions of water and the product air dried overnight. It is then suspended in 3L of hexane) filtered and washed with an additional 3L of hexane. The product is then vacuum dried overnight (50°C) 1 mm) to give 1354 g (94%) of NACA.
Acid Chloride (NACA-CIl - The reaction is carried out in a SL, 3-necked flask equipped with an addition funnel, mechanical stirrer and argon sweep. To a susperuion of 5428 (2.0 moles) of NACA in 2L of toluene is added (in a slow stream over 30 minutes) 476 g (4.0 moles) of thionyl chloride.
This mixture is stirred at room temperature for four hours during which time the solids dissolve. The solution is partially evaporated (30°C) 10 mm) to remove any excess thionyl chloride leaving 905g of NACA-CUtoluene solution (contains approximately 2 moles of NACA-CI). An IR spectrum confirms conversion of COOH to COCI.
(6-Nonanamidocapro I~xYbenzenesulfonate yACA-OBS) - The reactor is a 12L, 3-necked flask equipped with a condenser) mechanical stirrer and static argon supply. To the reactor are added 647g of the above NACA-CUtoluene solution ( I 43 moles), 6L of toluene and 310.8g ( 1.43 moles) of disodium p-phenolsulfonate (disodium p-phenolsulfonate is previously prepared and dried in a vacuum oven before use ( 1 I 0°C) 0.1 mm hg) 18 hours). This mixture is refluxed for 18 hours. After cooling to room temperature, the product is collected on a Buchner funnel and dried to give 725g of rnrde solids. The crude is taken up in 7L of refluxing 87:13 (v,v) 2 5 methanoUwater) filtered hot and allowed to recrystallize at room temperature.
The resulting precipitate is filtered and vacuum dried (50°C, 0.1 mm) for 18 hours to give 4108 (64% based on NACA) of light tan product. A trace of unreacted phenolsulfonate is indicated by the small doublets at 6.75 and 7.55 ppm in the 1 H spectrum Otherwise, the spectra are consistent with expected structure and no other impurities are evident.

A granular detergent compositions is prepared comprising the following ingredients.
m n nt Wei h8 t C 12 linear alkyl benzene sulfonate 22 Phosphate (as sodium tripolyphosphate) 30 '~1.6~.~1~
Sodium carbonate 14 Sodium silicate 3 Sodium percartionate 5 Ethylenediamine disuccinate cheliant (EDDS) 0.4 Sodium sulfate 5.5 (6-Nonanamidocaproyl)oxybenz~~nesulfonate 5 Minors, filler' and water Balance to 100%
'Can be selected from convenient materiuaals such as CaC03, talc) clay) silicates) and the like.
In testing the bleaching performance and effect on natural rubber washing machine parts) the following test method is used:
Aqueous crutcher mixes of heat and alkali stable components of the detergent compositions are prepared anjd spray-dried. The other ingredients are admixed so that the composition cokrtains the ingredients tabulated at the levels shown.
The detergent granules with blea~eh activator are added together with 5 Ib. (2.3 kg) of previously laundered fat~rics) including natural rubber articles such as elastic fabrics, to an automatic washing machine equipped with a natural rubber sump hose. Actual weighty of detergent and bleach activator are taken to provide a 950 ppm concenyration of the former and 50 ppm concentration of the latter in the 17 gallon (65 1) water-fill machine. The water used has 7 grains/gallon hardness and ~a; pH of 7 to 7.5 prior to (about 9 to about 10.5 aRa) addition of the detergent and bleaching system.
The fabrics are laundered at 35°C~ (95°F) for a full cycle (12 min.) and rinsed at 21 oC (70oF). The IaunderinB~ method is repeated for 2,000 wash cycles without rupture of) or significant dlamage to) the natural rubber pans, or damage to the natural rubber articles.
EXAMPI;.E III
A granular detergent composition is prepared comprising the following ingredients.
n n , Weightht%
Anionic alkyl sulfate 7 Nonionic surfactant Zeolite (0. I - I 0 micron) I p Trisodium citrate 2 SKS-6 silicate builder I p Acrylaie maleate polymer 4 (6-Nonanamidocaproyl~xybenzenesulfonate 5 Sodium percarbonate 15 Sodium carbonate 5 Ethylenediamine disuccinate chelant (EDDS) 0.4 Suds suppresser 2 E~~' 1. 5 Soil release agent 0.2 Minors) filler" and water Balance to 100%
' 1: I :1 mixture of proteax) lipax) and cellulase.
"Can be xleaed from convenient materials such as CaC03) talc, clay, silicates) and the like.
In testing the bleaching performance and effect on natural rubber washing machine parts) the following test method is used:
Aqueous rnrtcher mixes of heat and alkali stable components of the detergent composition are prepared and spray-dried. the other ingredients are admixed so that the composition contains the ingredients tabulated at the levels shown.
The detergent granules with bleach activator are added via the dispensing drawer together with 5 Ib. (2.3 kg) of previously laundered fabrics to an automatic washing machine equipped with a natural rubber sump hose.
Actual weights of detergent and bleach activator are taken to provide a 8,000 ppm concentration of the former and 400 ppm concentration of the latter in the 17 1 water-fill machine. The water used has 7 grains/gallon hardness and a pH
of 7 to 7.5 prior to (about 9 to about 10.5 at3er) addition of the detergent and bleaching rystem.
The fabrics are laundered at 40oC ( 104oF) for a full cycle (40 min. ) and rinxd at 21 oC (70oF). The laundering method is repeated for 2,000 wash rycles without rupture of, or significant damage to) the natural nrbber parts.
3o EXAMPLE IV
A detergent composition is prepared by a procedure identical to that of Example III, with the single exception that an equivalent amount of nonanoyloxybenzenesulfonate (HOBS) is substituted for the (6-Nonanamido-caproyl)oxybenzenesulfonate bleach activator in Example III. The laundering method of Example III is repeated for 1200 cycles at about which time the natural rubber sump hex ruptures.

EXAIyC LE V
A detergent composition is prepared by a procedure identical to that of Example III, with the single exception that an equivalent amount of benzoyloxybenzenesulfonate (BOBS) i:p substituted for the (6-Nonanamido-caproyl~xybenzenesulfonate bleach activator in Example III. The laundering method of Example III is repeated fore 1200 cycles at about which time the natural rubber sump hose ruptures.
E_~LE VI
A detergent composition is prepared by a procedure identical to that of Example III) with the exceptions that ~: I S% of a l : l mixture of tetraacetyl ethylene diamine and (6-Nonanamidbcaproyl)oxybenzenesulfonate bleach activator is substituted for the bleach acitivator in Example III and the amount of sodium percarbonate is 30%. The Maundering method of Example III is repeated for 2,000 rycles without rupt~rre of) or significant damage to, the natural rubber parts.

A detergent composition is prepared by a procedure identical to that of Example III, with the single exception ~khat I S% of a l : l mixture of benzoyl caprolactam and (6-Nonanamidocaproyl;'oxybenzenesulfonate is substituted for 2o the bleach activator in Example III and the amount of sodium percarbonate is 30%. The laundering method of Exar~tple 1II is repeated for 2,000 cycles without rupture of, or significant damaged to, the natural rubber parts.
EXAMPI~,E V111 A detergent composition is prepared by a procedure identical to that of .5 Example III, with an equivalent amolunt of a benzoxazin-type bleaching activator, as disclosed in U.S. Pstent 4,9166,723, Hodge et al, is substituted for the bleach activator in Example III. Thy laundering method of Example III is repeated for 2,000 rycles without ruptjure of, or significant damase to) the natural rubber parts.
3o EXAMP E tX
A detergent composition is prepared by a procedure identical to that of Example III) with the single exception tlhat 6% of a 1:1 mixture of (6-Nonan-amidocaproyl)oxybenzenesulfonate and ~k benzoxazin-type bleaching activator, as disclosed in U.S Patent 4,966,723) H~pdge et al) is substituted for the bleach 35 activator in Example 111. The laundering. method of Example III is repeated for WO 94/28104 ~ PCT/US94105370 :~1~ ~.'~
2,000 cycles without rupture of) or significant damage to, the natural rubber parts.
~, LE X
A detergent composition is preps~red by a procedure identical to that of 5 Example III) with the single exception t~tat 6% of a 1:1 mixture of tetraacetyl ethylene diamine and a benzoxazin-typie bleaching activator, as disclosed in U.S. Patent 4,966,723, Hedge et al) is ,substituted for the bleach activator in Example III. The laundering method of Example III is repeated for 2,000 cycles without rupture of) or significant yamage to) the natural rubber parts.
10 Method of Processing 'the Bleach Activators The bleach activators may be plrocessed with a range of organic and inorganic substance to achieve a rapid dispersion in the bleaching Liquor and to insure good stability in the detergent ccbmposition. The bleach activators are preferably employed in partiarlate form. i 15 An example of preferred caproluactam bleach activator particles is an agglomerate of about 65%) by weight,, benzoyl caprolactam; about 7% of a builder, such as aluminium silicate; about 15% sodium carbonate; about 9%
dispersant, such as a polyacrylate poly~tner; and about 4% of a solubilizing agent) such as a linear alkyl sulfonatie. Another example of a preferred 20 caprolactam bleach activator particle is ~n agglomerate of about 80% to about 85%, by weight, benioyl aprolactam ~ and about 15% to about 20% of a binder) such as tallow alcohol ethoxylate~) preferably TAE25.
An example of a preferred ar~ido-derived bleach activator particle comprises a 1:1:1 mixture of (6-octanajmidocaproyl)oxybenzenesulfonate) (6 decanamidocaproyl~xyben~enesulfonate~) and citric acid powder. The mixture is intimately mixed in a food mixer for 5~-10 minutes. To the resultant mixture is added tallow alcohol ethoxylate (TAE~25) nonionic surfactant at SOo C until granules are formed. Typically successful granulations are achieved with a ratio of bleach aaivator/citric acid solid mixtures:nonionic binding agent of 3.5:1. The resultant granules) ellipsodia~I and spherical in shape) are white and free flowing.
A typical particle composition i~~ about 40% to about 60%) preferably about 55%) by weight, of the bleach ac>Givator or mixture of bleach activators;
about 20% to about 40%) preferably ab6ut 25%, by weight, of citric acid; and about 15% to about 30%) preferably ab~put 20%, by weight of TAE25 binding agent. Alternatively, a 2:1 mixtmre of (6-decanamidocaproyl)oxyben-~16~.2:~1 zenesulfonate and citric acid powder. may be used. In this case, the composition on the granule is SS% bleayh activator, 2S% citric acid, and 20%
TAE2S binding agent. Other preferred organic binding agents include anionic surfactants (C 12 linear alkyl benzene ,~ulfonates)) polyethylene glycols) and TAESO.
The particle size of the resulting granules may be varied according to the desired performanceJstability. Fine panicles (<2S0 um) show improved solubility) though coarse particles (>~ 180 um) are more stable at high temperatures/moist environment. A tylpically preferred particle size range is 2S4-1180 um; particles conforming to thus specification show excellent stability end solubility. v ~XAMP~LE XI
A laundry bar suitable for hand~~washing soiled fabrics is prepared by standard extrusion processes and comprises the following:
m n n Weir C 12 linear alkyl benzene sulfonate 30 Phosphate (as sodium tripolypho;sphate) 7 Sodium carbonate 2S
Sodium pyrophosphate 7 Coconut monoethanolamide 2 Zeolite A (0.1-10 micron) S

Carboxymethylcellulose 0.2 Ethylenediamine disuccinate chel,itnt (EDDS) 0.4 Polyacrylate (m.w. 1400) 0.2 2 S (6-Nonanamidocaproyl)~xybenzelnesulfonateS

Sodium percarbonate' S

Brightener, perfume 0.2 Protease 0.3 CaS04 1 MgS04 1 Water 4 Filler" Balance to 100%
'Average particle size of 400 to 1200 miicrons.
"Can be selected from convenient nitaterials such as CaC03) talc) clay) silicates, and the like WO 94/28104 v ~ PCT/US94/05370 ~~~~~1~

The detergent laundry bars acre processed in conventional soap or detergent bar making equipment as cpmmonly used in the art: Testing is conducted following the testing mettwods in Example II. The laundering method is repeated for 2,000 wash cycles without rupture of) or significant damage to, the natural rubber parts) or namage to the natural rubber articles.

Claims (26)

1. A bleaching system comprising a peroxygen bleaching compound, preferably selected from the group consisting of perborate salts and percarbonate salts, and a bleach activator system selected from the group consisting of:
I) a) a bleach activator of formula i):

, 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; or mixture of a bleach activator of formula i) with a bleach activator of formula ii):

wherein R1 is H, alkyl, alkaryl, aryl, aralkyl, 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; and b) a nonamido-derived hydrophilic bleach activator, and II) a) a bleach activator of formula ii), and b) a non-amido-derived hydrophilic bleach activator of the N-acyl caprolactam type.

-23a-

2. A composition according to Claim 1 wherein R1 is an alkyl group containing from about 7 to about 10 carbon atoms, R2 contains from about 4 to about 5 carbon atoms, and L is selected from the group consisting of:

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

3. A composition according to Claim 1 wherein the hydrophilic bleach activator is a N-aryl caprolactam activator wherein the aryl moiety has the formula R1-CO- wherein R1 contains 6 or less carbon atoms.

4. A composition according to Claim 3 wherein the hydrophilic caprolactam bleach activator is benzoyl caprolactam.

5. A composition according to Claim 1 wherein the bleach activator is .

6. A composition according to Claim 1 wherein the hydrophilic bleach activator is tetraacetyl ethylene diamine.

7. A composition according to Claim 1 wherein the the peroxygen bleaching compound is selected from perborate salts and percarbonate salts.

8. A composition according to Claim 1 which additionally comprises a chelant.

9. A composition according to Claim 8 wherein the chelant is an ethylenediamine disuccinate chelant or an aminophosphonate chelant.

10. A composition according to Claim 1 in the form of a laundry detergent which additionally comprises. detersive surfactants, builders and detersive adjunct ingredients.

11. 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 bleaching system according to Claim 1, such that said natural rubber parts of said machine are substantially undamaged by the bleaching system.

12. A method according to Claim 11 wherein the bleaching system comprises a bleach activator which reacts in said aqueous liquor to yield a peroxyacid of the general formulae:

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

13. A method according to Claim 12 wherein said aqueous liquor further comprises conventional detergent ingredients; said bleaching system comprising:
a) at least about 0.1%, by weight, of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous liquor;
and b) at least about 0.1%, by weight, of a bleach activator selected from the goup consisting of:

,~~ or mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group containing from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene or alkarylene goup containing from about 1 to about 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl goup containing from about 1 to about 10 carbon atoms, and L is a leaving goup; and ~

wherein R1 is H, alkyl, alkaryl, aryl, aralkyl, 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, such that the molar ratio of hydrogen peroxide yielded by a) to bleach activator b) is greater than about 1Ø

14. A method according to Claim 13 wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 contains from about 1 to about 8 carbon atoms, and R5 is H or methyl.

15. A method according to Claim 14 wherein R1 is an alkyl group containing from about 7 to about 10 carbon atoms and R2 contains from about 4 to about 5 carbon atoms.

16. A method according to Claim 13 wherein 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 about 1 to about 8 carbon atoms, R4 is H
or R3, and Y is H or a solubilizing group.

17. A method according to Claim 16 wherein Y is selected from the group consisting of: -SO3-M+, -CO2-M+, -SO4-M+, -N+(R3)4X- and 0<-N(R3)3 and mixtures thereof wherein R3 is an alkyl chain containing from 1 to about 4 carbon atoms, M is a ration which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.

18. A method according to Claim 16 wherein L is selected from the group consisting of:

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

19. A method according to Claim 13 wherein the bleach activator is .

20. A method according to Claim 13 wherein the conventional detergent ingredients comprise from about 5% to about 80%, by weight, of a detersive surfactant.

21. A method according to Claim 20 wherein the conventional detergent ingredients further comprise from about 5% to about 80%, by weight, of a detersive builder and from 0% to about 20%, by weight, of conventional detersive adjunct materials.

22. A method according to Claim 13 wherein the peroxygen bleaching compound is selected from the group consisting of sodium perborate monohydrate, sodium percarbonate, sodium perborate tetrahydrate, sodium pyrophosphate peroxy-hydrate, urea peroxy-hydrate, sodium peroxide and mixtures thereof.

23. A composition according to Claim 1 wherein said bleach activators are in particulate form.

24. A composition according to Claim 23 wherein said bleach activator particle comprises shout 40% to about 60%, by weight, of a 1:1 mixture of (6-octanamidocaproyl)oxybenzenesulfonate and (6-decanamidocaproyl)oxybenzenesulfonate; about 20% to about 40%, by weight, citric acid; and about 15% to about 30%, by weight, tallow alcohol ethoxylate nonionic surfactant.

25. A composition according to Claim 23 wherein said bleach activator particle comprises about 65% benzoyl caprolactam, about 7%
aluminium silicate, about 15% sodium carbonate, about 9%
polyacrylate poymer, and about 4% linear alkyl sulfonate.

26. A composition according to Claim 23 wherein said particle comprises about 80% benzoyl caprolactam and about 20% tallow alcohol ethoxylate nonionic surfactant.