Bleaching detergent compositions comprising bleach activators effective at low perhydroxyl concentrations

Bleaching detergent compositions comprising particular bleach activators are provided. Excellent bleaching is secured through the selection of bleach activators which operate successfully under mildly alkaline washing conditions or in the presence of reduced levels of hydrogen peroxide.

FIELD OF THE INVENTION 
The present invention relates to improved bleaching detergent compositions 
comprising bleach activators. The bleach activators improve bleaching by 
hydrogen peroxide sources such as perborate. 
BACKGROUND OF THE INVENTION 
The formulation of detergent compositions which effectively remove a wide 
variety of soils and stains from fabrics under wide-ranging usage 
conditions, for example in a range of Pacific rim countries, remains a 
considerable challenge to the laundry detergent industry. The problems 
associated with the formulation of truly effective cleaning and bleaching 
compositions have been exacerbated by legislation which limits the use of 
effective ingredients such as phosphate builders in many regions of the 
world. 
Most conventional cleaning compositions contain mixtures of various 
detersive surfactants to remove a wide variety of soils and stains from 
surfaces. In addition, various detersive enzymes, soil suspending agents, 
non-phosphorus builders, optical brighteners, and the like may be added to 
boost overall cleaning performance. Many fully-formulated cleaning 
compositions contain oxygen bleach, which can be a perborate or 
percarbonate compound. While quite effective at high temperatures, 
perborates and percarbonates lose much of their bleaching function at the 
low to moderate temperatures increasingly favored in consumer product use 
for energy efficiency or other reasons, e.g., convenience of hand-washing. 
Accordingly, various bleach activators such as tetraacetylethylenediamine 
(TAED) and nonanoyloxybenzenesulfonate (NOBS) have been developed to 
potentiate the bleaching action of perborate and percarbonate across a 
wide temperature range. NOBS is particularly effective on "dingy" fabrics. 
A limitation with activators such as the widely commercialized TAED is that 
the wash solution or liquor should have a pH of about 10 or higher for 
best results. Since soils, especially from foods, are often acidic, 
detergent products are frequently quite alkaline or are buffered 
sufficiently to maintain a high pH so the bleach activator system can 
operate effectively throughout the wash. However, this need runs counter 
to providing milder formulations which could be improved in their 
compatibility with fabrics, glassware and/or skin. In cleaning operations 
below pH 10, many of the existing bleach activators lose their 
effectiveness or undergo competeing side reactions which produce 
ineffective byproducts. 
The search, therefore, continues for more effective activator materials, 
especially for use in mildly alkaline washing liquors or with decreased 
levels of perborate or other sources of hydrogen peroxide. Improved 
activator materials should be safe, designed to interact effectively with 
troublesome soils and stains, and will preferably be very efficient. 
Various activators have been described in the literature. Many are 
esoteric and expensive and thus difficult to commercialize, especially in 
certain countries, as in parts of Asia, where local sources of raw 
materials may not be available. 
It has now been determined that certain selected bleach activators are 
unexpectedly effective in removing soils and stains from fabrics and hard 
surfaces such as dishes even under low alkaline wash conditions or with 
decreased levels of hydrogen peroxide. These activators also have 
advantageously high ratios of rates of perhydrolysis to hydrolysis and of 
perhydrolysis to diacylperoxide formation. Without being limited by 
theory, these unusual rate ratios lead to a number of significant benefits 
for the instant activators, including increased efficiency, avoidance of 
wasteful byproduct formation in the wash, increased color compatibility, 
increased enzyme compatibility, and better stability on storage. 
When formulated as described herein, bleaching detergent compositions are 
provided using the selected bleach activators to remove soils and stains 
under a variety of conditions, including high-soil conditions, with 
excellent results. The activators are designed or selected to function 
well over a wide range of washing or soaking temperatures. In short, 
bleaching detergent compositions herein provide a substantial advance over 
those known in the art, as will be seen from the disclosures hereinafter. 
BACKGROUND ART 
Bleach activators of various types are described in U.S. Pat. Nos. 
4,545,784; 4,013,575; 3,075,921; 3,637,339; 3,177,148; 3,042,621; 
3,812,247; 3,775,332; 4,778,618; 4,790,952; EP 257,700; WO 94/18,299; WO 
94/18,298; WO 93/20,167; WO 93/12,067; and in JP 02115154. Other 
references include Aikawa CA 85:1086z; Stehlicek CA 108:187402w; Ishida CA 
88:169981y; Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 7, 4th 
Ed., 1993, pp. 1072-1117; Kirk Othmer, Encyclopedia of Chemical 
Technology, Vol. 4, 4th Ed., 1994, pp. 271-299; Kirk Othmer, Encyclopedia 
of Chemical Technology, Vol. 9, 4th Ed., 1993, pp. 567-620. 
SUMMARY OF THE INVENTION 
The present invention provides a bleaching detergent composition having low 
soil level resistivity comprising (a) from about 0.1% to about 20%, 
preferably from about 0.2% to about 10%, more preferably from about 0.4% 
to about 4% of a bleach activator having a perhydrolysis selectivity 
coefficient, Kp/K.sub.D, of at least about 5, preferably at least about 
20, more preferably at least about 50, and a low-pH 
perhydrolysis-efficiency coefficient of at least about 0.15, preferably at 
least about 0.30, most preferably at least about 0.5; and (b) from about 
0.2% to about 40%, preferably from about 0.5% to about 35%, more 
preferably from about 1% to about 25%, of a hydrogen peroxide source; the 
quantities of (b) being expressed on a weight basis counting the entire 
hydrogen peroxide source as distinct from a molar or "available oxygen" 
basis which may be used from time to time, as indicated, elsewhere herein. 
The terms "soil level resistivity", "perhydrolysis selectivity 
coefficient" and "low pH perhydrolysis efficiency coefficient" are defined 
in detail hereinafter. 
Preferred bleach activators for component (a) include, but are not limited 
to any of the following: p-nitrobenzoyl caprolactam; 
p-nitrobenzoylvalerolactam; linear or branched C.sub.2 -C.sub.9 
alkylsulfonylbenzoylcaprolactam; linear or branched C.sub.2 -C.sub.9 
alkylsulfonylbenzoylvalerolactam; linear or branched C.sub.2 -C.sub.9 
alkyloxysulfonylbenzoylcaprolactam; linear or branched C.sub.2 -C.sub.9 
alkyloxysulfonylbenzoylvalerolactam; linear or branched C.sub.2 -C.sub.9 
alkyl(amino)sulfonylbenzoylcaprolactam; linear or branched C.sub.2 
-C.sub.9 alkyl(amino)sulfonylbenzoylvalerolactam; 2-fliroylcaprolactam; 
2-furoylvalerolactam; 3-furoylcaprolactam; 3-furoylvalerolactam; 
5-nitro-2-furoylcaprolactam; 5-nitro-2-furoylvalerolactam; 
1-naphthylcaprolactam; 1-naphthylvalerolactam; and mixtures thereof. More 
preferably in these embodiments, the performance-enhanced bleach activator 
is selected from the group consisting of linear or branched C.sub.2 
-C.sub.9 alkylsulfonylbenzoylcaprolactam; linear or branched C.sub.2 
-C.sub.9 alkylsulfonylbenzoyl-valerolactam; linear or branched C.sub.2 
-C.sub.9 alkyloxysulfonylbenzoylcaprolactam; linear or branched C.sub.2 
-C.sub.9 alkyloxysulfonylbenzoylvalerolactam; linear or branched C.sub.2 
-C.sub.9 alkyl(amino)-sulfonylbenzoylcaprolactam; linear or branched 
C.sub.2 -C.sub.9 alkyl(amino)sulfonylbenzoyl-valerolactam; 
2-furoylcaprolactam; 2-furoylvalerolactam; 3-furoylcaprolactam; 
3-furoylvalerolactam; 5-nitro-2-furoylcaprolactam; 
5-nitro-2-furoylvalerolactam; and mixtures thereof. 
In preferred embodiments, bleaching detergent compositions are provided 
wherein said components (b) and (a) are at a ratio of from about 3:1 to 
about 20:1, as expressed on a basis of (b):(a) in units of moles H.sub.2 
O.sub.2 delivered by said hydrogen peroxide source to moles bleach 
activator. 
Compositions of the invention may further comprise (c) from about 0.1% to 
about 50% of pH-reducing nonsoap detersive ingredients; such ingredients 
are a particularly convenient solution to the problem of offsetting the 
upward-buffering tendencies of common hydrogen peroxide sources such as 
sodium perborate salts. Such offsetting may be desirable in certain 
embodiments, e.g., for mild, skin-compatible compositions. 
In certain preferred embodiments, there may be added from about 0.01% to 
about 5% of a soil release polymer, for its fabric-care advantages. 
In a highly preferred embodiment, suitable pH-reducing nonsoap detersive 
ingredients herein consist essentially of from about 1% to about 25% of 
one or more members selected from the group consisting of: 
(i) nonsoap ionic detersive surfactants; 
(ii) polymeric dispersants; 
(iii) transition-metal chelants; and 
(iv) mixtures thereof 
To further illustrate, said pH-reducing nonsoap detersive ingredient may be 
an ionic detersive surfactant selected from the group consisting of 
anionic detersive surfactants in at least partially acidic form; semipolar 
surfactants; zwitterionic surfactants; and mixtures thereof. 
The advantage of the above component is to combine in a single material the 
cleaning functionality of a surfactant with the ability to "tune" the 
formulation so that it delivers a specific pH range. To be clear, without 
the selected bleach activators used herein, such tuning would negatively 
affect bleaching performance. 
Surfactants which are normally neutral may also be added for their usual 
cleaning function, though it is self-evident that such surfactants do not 
have built-in pH lowering effects. A preferred surfactant which may also 
be added to the composition but which does not markedly alter pH is a 
sugar-derived detersive surfactant such as an alkyl N-methylglucosamide. 
Ethoxylated nonionic detersive surfactants are likewise "neutral" for the 
purposes of the present invention. 
Preferred embodiments of the bleaching detergent compositions herein have 
solid form. Preferred compositions include granules. For storage reasons, 
especially in hot countries such as Saudi Arabia, it is preferred that the 
selected bleach activator has a melting-point of about 30.degree. C. or 
higher, preferably, 50.degree. C. or higher. 
The instant bleaching detergent compositions may further comprise an 
alkaline detergent builder, such as a phosphate salt, preferably at a 
level not in excess of about 35%. 
In other highly preferred embodiments of the bleaching detergent 
composition, the alkaline hydrogen peroxide source is a sodium perborate 
such as sodium perborate monohydrate or sodium perborate tetrahydrate, and 
the pH-reducing system of compatible nonsoap detersive ingredients is 
present at a level of from about 1% to about 12%. 
Highly desirable, as noted, is the further inclusion of a soil release 
polymer. When present, the soil release polymer is preferably a member 
selected from the group consisting of nonionic soil release polymers; 
sulfo-end-capped soil release polymers; and mixtures thereof. Such 
polymers are defined and illustrated in more detail hereinafter using the 
equivalent terms "polymeric soil release agent" or "soil release agent". 
In a further non-limiting illustration, the invention provides a solid-form 
detergent composition delivering an in-use pH in the range from about 7 to 
about 9.5, comprising: from about 0.4% to about 4% of a bleach activator 
having a perhydrolysis selectivity coefficient of 5 or greater and a 
low-pH perhydrolysis-efficiency coefficient of 0.3 or higher; and, as 
formulated, from about 1% to about 12% of an at least partially acidic 
nonsoap detersive surfactant. Such a composition may further comprise from 
about 0.1 to about 10% of a member selected from the group consisting of 
sodium phosphate builder salts, sodium polycarboxylate builder salts, and 
mixture thereof; and about 10% or greater of a member selected from the 
group consisting of sodium chloride, sodium sulfate and mixtures thereof; 
optionally, the composition may further include a conventional 
alkanoyloxybenzenesulfonate bleach activator or a conventional 
tetraacetylethylenediamine bleach activator. 
Bleaching detergent compositions of this invention may include additional 
detergent additives including one or more of the following ingredients: 
anti-redeposition or anti-encrustation polymers, transition-metal 
chelants, builders, flourescent whitening agents, dye transfer inhibitors, 
perfumes, colorants and fillers. Compositions of this invention are 
typically formulated below drycleaning-useful levels of any organic 
solvent. Preferably the compositions are substantially free from organic 
solvents. Suitable builders are selected from the group consisting of 
phosphate builders including but not limited to sodium tripolyphosphate, 
tetrasodium pyrophosphate, disodium diacid pyrophosphate, citrate, layered 
silicate, zeolite A, zeolite P in its various modifications, and mixtures 
thereof. 
In preferred embodiments, the bleaching compositions deliver an aqueous pH 
in the range from about 6.5 to about 9.5, more preferably from about 7 to 
about 9, still more preferably from about 7.5 to about 8.5, and the level 
of source of hydrogen peroxide is sufficient to provide a perhydroxyl ion 
concentration, as measured at a pH of about 7.5, of about 10.sup.-4 to 
about 10.sup.-10 molar, more preferably about 10.sup.-5 to about 10.sup.-8 
molar. 
The present invention has numerous advantages, including, but not limited 
to, improved bleaching in lower pH, skin-compatible handwash formulations 
for laundering fabrics, which can have granule or laundry bar form. 
By "effective amount" herein is meant an amount which is sufficient, under 
whatever comparative test conditions are employed, to enhance cleaning of 
a soiled surface. Likewise, the term "catalytically effective amount" 
refers to an amount which is sufficient under whatever comparative test 
conditions are employed, to enhance cleaning of a soiled surface. 
All percentages, ratios and proportions herein are by weight, unless 
otherwise specified. All documents cited are, in relevant part, 
incorporated herein by reference. 
DETAILED DESCRIPTION OF THE INVENTION 
Soil Level Resistivity--It is well known by those skilled in the art that 
many soils typically encountered in detergent applications are effectively 
acidic in nature. As such, the type and amount of soil encountered may 
significantly lower the in-use pH of a detergent formulation. Common body 
soils, for example, can include sebacious fatty acids, citric acid, lactic 
acid and the like as well as triglyceride esters which can hydrolyze in an 
alkaline aqueous environment to produce additional carboxylic acid 
species. The response of a detergent formulation to the introduction of 
acidic components can be gauged by measuring the change in pH of a 
standard solution of the formulation upon addition of a model acid, acetic 
acid. 
The "Soil Level Resistivity" (SLR) of a product is determined as follows: A 
3500 ppm product standard solution is prepared by dissolving 3.50 g of 
product in distilled, deionized water (at 25.degree. C.) to a total weight 
of 1 kg. The solution is stirred for 30 minutes and the pH measured 
immediately thereafter. The measured pH is defined as pH.sub.i. After 
determining pH.sub.i, 30 ml of an acetic acid solution (prepared by 
diluting 1 ml of glacial acetic acid with distilled, deionized water to a 
total volume of 1000 ml) is added to said product standard solution and 
the resulting mixture is stirred for 5 minutes, after which a second pH 
(pH.sub.f) is measured. 
The soil level resistivity, denoted as .sigma., is defined by the equation 
EQU .sigma.=10.times.(.theta./.GAMMA.): 
where 
EQU .GAMMA..times.pH.sub.i -pH.sub.f, 
EQU .theta.=.delta..sup.2 /pH.sub.i, 
and wherein, when pH.sub.i .gtoreq.pH.sub.c, 
EQU .delta.=pH.sub.i -pH.sub.c, 
and when pH.sub.i &lt;pH.sub.c, .delta.=0. Said pH.sub.c is the critical pH, 
given by 
EQU pH.sub.c =pK.sub.a.sbsb.peracid +.DELTA.pK.sub.c 
where .DELTA.pK.sub.c is the critical .DELTA.pK given by 
EQU .DELTA.pK.sub.c = 100(1/pK.sub.a.sbsb.peracid) -(1/pH.sub.pref)! 
wherein pK.sub.a.sbsb.peracid is the aqueous pK.sub.a of the peracid 
species present in the standard solution, and pH.sub.pref is the preferred 
pH, set equal to the midpoint of the most preferred in-use wash pH range 
of 7.5-8.5. When two or more peracid species are present, the lowest 
pK.sub.a.sbsb.peracid value is used to calculate .delta.. 
The soil level resistivity of any particular detergent formulation can be 
designated based on its .sigma. value as shown in the table below. 
______________________________________ 
SLR Designation .sigma. Value 
______________________________________ 
high .sigma. &gt; 25 
moderate 10 &lt; .sigma. .ltoreq. 25 
low .sigma. .ltoreq. 10 
______________________________________ 
Performance Enhanced Bleach Activator Component--Bleaching detergent 
compositions of the present invention comprise a particular bleach 
activator component. The essential activator is selected to have 
particular properties so as to be more effective in promoting bleaching 
under certain use conditions in which TAED or similar conventional bleach 
activators are relatively inefficient and ineffective. 
A preferred group of essential activators comprises compounds having one or 
more moieties RC(O)-- which produce a peracid RC(O)--OOH on perhydrolysis 
(reaction with perhydroxyl, .sup.- OOH). R is selected such that the 
difference in aqueous pK.sub.a between acetic acid and the carboxylic acid 
analog, RC(O)OH, of said peracid is at least 0.6, preferably at least 
about 1.2. When it is stated that the difference in aqueous pK.sub.a 
between acetic acid and the carboxylic acid analog, RC(O)OH, of a peracid 
is at least 0.6, the following subtraction, in the indicated order, is 
made: pK.sub.a (CH.sub.3 C(O)OH)--pK.sub.a (RC(O)OH). 
These performance-enhanced bleach activators also have a low pH 
perhydrolysis efficiency coefficient (a practical measure of peracid 
formation further defined hereinafter) of greater than about 0.15, 
preferably greater than about 0.3, and a ratio kp/k.sub.D .gtoreq.5, more 
preferably kp/k.sub.D .gtoreq.30, still more preferably kp/k.sub.D 
.gtoreq.50, wherein kp is the rate constant for perhydrolysis of the 
performance-enhanced bleach activator and k.sub.D is the rate constant for 
the formation of a diacylperoxide, RC(O)OOC(O)R, from the 
performance-enhanced bleach activator. 
The activators herein preferably comprise one or more moieties, L, which 
act as leaving groups on perhydrolysis. Thus, preferred performance 
enhanced bleach activators herein have the formula RC(O)--L. 
Preferred leaving groups, L, comprise at least one tri-coordinate nitrogen 
atom covalently connecting L to RC(O)--. Furthermore, the preferred 
performance-enhanced bleach activators are capable of forming a maximum of 
one mole equivalent of said peracid on perhydrolysis and have k.sub.H 
.ltoreq.10 M.sup.-1 s.sup.-1 and a ratio kp/k.sub.H .gtoreq.1, more 
preferably kp/k.sub.H .gtoreq.2, wherein k.sub.H is the rate constant for 
hydrolysis of the performance-enhanced bleach activator and kp is said 
rate constant for perhydrolysis. 
In general, R and L can independently be neutral or can be charged either 
positively or negatively. In preferred compositions, both R and L are 
neutral wherein L is typically selected from suitably substituted or 
unsubstituted lactams, 2-alkyl 4,5- dihydroimidazoles, and mixtures 
thereof, and R is illustrated by p-nitrophenyl or, more preferably, an 
alkylsulfonylphenyl moiety. Suitable R moieties are illustrated at length 
hereinafter. 
In preferred embodiments, R can be connected to --C(O)-- through a carbon 
atom which forms part of an aromatic ring, and L can be selected such that 
its conjugate acid, HL, has an aqueous pK.sub.a in the range from greater 
than about 13 to less than about 17. 
In other highly preferred embodiments, the performance-enhanced bleach 
activator as a whole, or simply its leaving group, L, is free from any 
heterocyclic moiety wherein a hydrogen atom is attached to a carbon atom 
that is alpha to both a carbonyl group and a multivalent heteroatom. 
In highly preferred embodiments, these compositions further comprise a 
bleach catalyst at the art-disclosed levels. Such compositions have 
particularly significant bleaching performance enhancement as compared 
with otherwise identical compositions in which a conventional bleach 
activator such as TAED is used in place of the performance-enhanced bleach 
activator. 
This invention also includes bleaching detergent compositions comprising 
novel, performance-enhanced bleach activator compounds having the formula 
RC(O)--L, wherein L is selected from the group consisting of lactams and 
4,5-dihydroimidazoles; R is selected from the group consisting of 
substituted phenyl having more than one chloro, bromo or nitro 
substituent; furan or substituted furan having one or more chloro, bromo, 
nitro, alkylsulfonyl or arylalkylsulfonyl substituents; 1-naphthyl; 
substituted 1-naphthyl; or substituted 2-naphthyl having one or more 
chloro, bromo or nitro substituents; 
##STR1## 
and mixtures thereof; wherein in each structure a is independently 0 or 1, 
b is 0 or 1, and A is selected from O and NR.sup.2 wherein R.sup.2 is H or 
methyl; and wherein when a is 1 and A is 0, R.sup.1 is selected from 
alkyl, arylalkyl, alkoxy, aryloxy, alkylamino, and arylamino; when a is 1 
and A is other than O, R.sup.1 is selected from alkyl and arylalkyl. 
Compositions comprising these novel compounds are also included in the 
scope of this invention. 
Moieties RC(O)--In preferred bleach activators useful herein, R is 
nonlimitingly illustrated by electronegatively substituted phenyl selected 
from the group consisting of p-chlorophenyl, m-chlorophenyl, 
p-nitrophenyl, 3,5-dichlorophenyl, and 3,5-dinitrophenyl, and mixtures 
thereof. In yet other preferred embodiments, R is selected from 
alkylsulfonylphenyl, arylalkylsulfonylphenyl, alkylsulfonyl naphthyl, 
arylalkylsulfonyl-naphthyl, and mixtures thereof. Note that when naphthyl 
is selected, unsubstituted 1-naphthyl or substituted 1- or 2-naphthyl is 
preferred. Other examples of preferred bleach activators include those 
wherein R is a substituted or unsubstituted furan, and wherein R is 
substantially free from chloro- or nitro- substituents. 
Leaving Groups--The L moieties in the performance-enhanced bleach 
activators useful in this invention are preferably selected from the group 
consisting of unsubstituted lactams, substituted lactams, substituted or 
unsubstituted 2-alkyl 4,5-dihydroimidazoles, and mixtures thereof. 
Particularly preferred examples of L are those selected from the group 
consisting of: 
##STR2## 
Novel Performance-Enhanced Bleach Activator Compounds--In preferred novel 
bleach activator compounds of this invention, L is as indicated supra and 
R is selected from the group consisting of: 
(I): 
##STR3## 
wherein a is independently 0 or 1, b is 0 or 1, A is selected from O and 
NR.sup.2 wherein R.sup.2 is H or methyl; when a is 0 or when a is 1 and A 
is O, R.sup.1 is selected from alkyl, arylalkyl, alkoxy, aryloxy, 
alkylamino, and arylamino; when a is 1 and A is other than O, R.sup.1 is 
selected from alkyl and arylalkyl; and 
(II) furan or substituted furan, having the formula: 
##STR4## 
wherein T is selected from the group consisting of H, NO.sub.2, Br, alkyl, 
and arylalkyl. 
In a highly preferred embodiment of the performance boosting bleach 
activator, L is preferably selected from the group consisting of: 
##STR5## 
and R is selected from the group consisting of: 
##STR6## 
wherein R1 is selected from alkyl, arylalkyl, alkoxy, aryloxy, alkylamino, 
and aryl-amino; and T is selected from the group consisting of H, Br, and 
NO.sub.2. Compositions comprising these novel compounds are also included 
in the scope of this invention. 
pK.sub.a Rate and Perhydrolysis Criticalities--In accordance with the 
present invention, there are provided bleaching compositions wherein the 
bleach activators are required to respect criticalities of pK.sub.a and 
criticalities relating to rates of perhydrolysis, hydrolysis and 
diacylperoxide formation. Furthermore, perhydrolysis effciency is 
important in selecting the bleach activator. All of these criticalities 
will be better understood and appreciated in light of the following 
disclosure. 
pK.sub.a Value--The acids in which organic chemists have traditionally been 
interested span a range, from the weakest acids to the strongest, of about 
60 pK units. Because no single solvent is suitable over such a wide range, 
establishment of comprehensive scales of acidity necessitates the use of 
several different solvents. Ideally, one might hope to construct a 
universal acidity scale by relating results obtained in different solvent 
systems to each other. Primarily because solute-solvent interactions 
affect acid-base equilibria diffently in different solvents, it has not 
proven possible to establish such a scale. 
Water is taken as the standard solvent for establishing an acidity scale. 
It is convenient, has a high dielectric constant, and is effective at 
solvating ions. Equilibrium acidities of a host of compounds (e.g., 
carboxylic acids and phenols) have been determined in water. Compilations 
of pK data may be found in Perrin, D. D. "Dissociation Constants of 
Organic Bases in Aqueous Solution"; Butterworths: London, 1965 and 
Supplement, 1973; Serjeant, E. P.; Dempsey, B. "Ionisation Constants of 
Organic Acids in Aqueous Solution"; 2nd ed., Pergammon Press: Oxford, 
1979. Experimental methods for determining pK.sub.a values are described 
in the original papers. The pK.sub.a values that fall between 2 and 10 can 
be used with a great deal of confidence; however, the further removed 
values are from this range, the greater the degree of skepticism with 
which they must be viewed. 
For acids too strong to be investigated in water solution, more acidic 
media such as acetic acid or mixtures of water with perchloric or sulfuric 
acid are commonly employed; for acids too weak to be examined in water, 
solvents such as liquid ammonia, cyclohexylamine and dimethylsulfoxide 
have been used. The Hammett H.sub.o acidity function has allowed the 
aqueous acidity scale, which has a practical pK.sub.a range of about 0-12, 
to be extended into the region of negative pK.sub.a values by about the 
same range. The use of H.sub.-- acidity functions that employ strong bases 
and cosolvents has similarly extended the range upward by about 12 
pK.sub.a units. 
The present invention involves the use of leaving groups the conjugate 
acids of which are considered to be weak; they possess aqueous pK.sub.a 
values greater than about 13. To establish only that a given compound has 
an aqueous pK.sub.a above about 13 is straightforward. As noted above, 
values much above this are difficult to measure with confidence without 
resorting to the use of an acidity function. The measurement of the 
acidity of weak acids using the H.sub.-- method, which has the advantage 
of an aqueous standard state, is suitable for determining if the conjugate 
acid, HL, of leaving group, L, has an aqueous pK.sub.a of greater than 
about 13 to less than about 17. Hovever, it is restricted in that (1) it 
requires extrapolation across varying solvent media and (2) errors made in 
determining indicator pK.sub.a values are cumulative. For these and other 
reasons, Bordwell and co-workers have developed a scale of acidity in 
dimethylsulfoxide (DMSO). This solvent has the advantage of a relatively 
high dielectric constant (.epsilon.=47); ions are therefore dissociated so 
that problems of differential ion pairing are reduced. Although the 
results are referred to a standard state in DMSO instead of in water, a 
link with the aqueous pK.sub.a scale has been made. When acidities 
measured in water or on a water-based scale are compared with those 
measured in DMSO, acids whose conjugate bases have their charge localized 
are stronger acids in water; acids whose conjugate bases have their charge 
delocalized over a large area are usually of comparable strength. Bordwell 
details his findings in a 1988 article (Acc. Chem. Res. 1988, 21, 
456-463). Procedures for measurement of pK.sub.a in DMSO are found in 
papers referenced therein. 
Definitions of k.sub.H, k.sub.p, and k.sub.D --In the expressions given 
below, the choice of whether to use the concentration of a nucleophile or 
of its anion in the rate equation was made as a matter of convenience. One 
skilled in the art will realize that measurement of solution pH provides a 
convenient means of directly measuring the concentration of hydroxide ions 
present. One skilled in the art will further recognize that use of the 
total concentrations of hydrogen peroxide and peracid provide the most 
convenient means to determine the rate constants k.sub.p and k.sub.D. 
The terms, such as RC(O)L, used in the following definitions and in the 
conditions for the determination of k.sub.H, k.sub.p and k.sub.D, are 
illustrative of a general bleach activator structure and are not limiting 
to any specific bleach activator structure herein. 
Definition of k.sub.H 
EQU RC(O)L+HO.sup.- .fwdarw.RC(O)O.sup.- +HL 
The rate of the reaction shown above is given by 
EQU Rate=k.sub.H RC(O)L!HO.sup.- ! 
The rate constant for hydrolysis of bleach activator (k.sub.H) is the 
second order rate constant for the bimolecular reaction between bleach 
activator and hydroxide anion as determined under the conditions specified 
below. 
Definition of k.sub.p 
EQU RC(O)L+H.sub.2 O.sub.2 .fwdarw.RC(O)O.sub.2 H+HL 
The rate of the reaction shown above is given by 
EQU Rate=k.sub.p RC(O)L!H.sub.2 O.sub.2 !.sub.T 
where H.sub.2 O.sub.2 !.sub.T represents the total concentration of 
hydrogen peroxide and is equal to H.sub.2 O.sub.2 !+HO.sub.2.sup.- !. 
The rate constant for perhydrolysis of bleach activator (k.sub.p) is the 
second order rate constant for the bimolecular reaction between bleach 
activator and hydrogen peroxide as determined under the conditions 
specified below. 
Definition of K.sub.D 
EQU RC(O)L+RC(O)O.sub.2 H.fwdarw.RC(O)O.sub.2 C(O)R+HL 
The rate of the reaction shown above is given by 
EQU Rate=k.sub.D RC(O)L!RC(O)O.sub.2 H!.sub.T 
where RC(O)O.sub.2 H!.sub.T represents the total concentration of peracid 
and is equal to 
EQU RC(O)O.sub.2 H!+RC(O)O.sub.2.sup.- !. 
The rate constant for the formation of a diacylperoxide from the bleach 
activator (k.sub.D), the second order rate constant for the bimolecular 
reaction between bleach activator and peracid anion, is calculated from 
the above defined k.sub.D'. The value for k.sub.D' is determined under 
the conditions specified below. 
Definition of Perhydrolysis Selectivity Coefficient--Perhydrolysis 
selectivity coefficient is defined as the ratio K.sub.p /K.sub.D wherein 
K.sub.p and K.sub.D are as defined as above. 
Conditions for the Determination of Rate Constants 
Hydrolysis--A set of experiments is completed to measure the rate of 
hydrolysis of a bleach activator RC(O)L in aqueous solution at total ionic 
strength of 1M as adjusted by addition of NaCl. The temperature is 
maintained at 35.0.degree..+-.0.1.degree. C. and the solution is buffered 
with NaHCO.sub.3 +Na.sub.2 CO.sub.3. A solution of the activator (RC(O)L! 
=0.5 mM) is reacted with varying concentrations of NaOH under stopped-flow 
conditions and the rate of reaction is monitored optically. Reactions are 
run under pseudo first-order conditions to determine the bimolecular rate 
constant for hydrolysis of bleach activator (k.sub.H). Each kinetic run is 
repeated at least five times with about eight different concentrations of 
hydroxide anions. All kinetic traces give satisfactory fits to a 
first-order kinetic rate law and a plot of the observed first-order rate 
constant versus concentration of hydroxide anion is linear over the region 
investigated. The slope of this line is the derived second order rate 
constant k.sub.H. 
Perhydrolysis--A set of experiments is completed to measure the rate of 
perhydrolysis of a bleach activator RC(O)L in aqueous solution at pH=10.0 
with constant ionic strength of 1M as adjusted by addition of NaCl. The 
temperature is maintained at 35.0.degree..+-.0.1.degree. C. and the 
solution is buffered with NaHCO.sub.3 +Na.sub.2 CO.sub.3. A solution of 
the activator (RC(O)L!=0.5 mM) is reacted with varying concentrations of 
sodium perborate under stopped-flow conditions and the rate of reaction is 
monitored optically. Reactions are run under pseudo first-order conditions 
in order to determine the bimolecular rate constant for perhydrolysis of 
bleach activator (kp). Each kinetic run is repeated at least five times 
with about eight different concentrations of sodium perborate. All kinetic 
traces give satisfactory fits to a first-order kinetic rate law and a plot 
of the observed first-order rate constant versus total concentration of 
hydrogen peroxide is linear over the region investigated. The slope of 
this line is the derived second order rate constant kp. One skilled in the 
art recognizes that this rate constant is distinct from, but related to, 
the second order rate constant for the reaction of a bleach activator with 
the anion of hydrogen peroxide (k.sub.nuc). The relationship of these rate 
constants is given by the following equation: 
EQU k.sub.nuc =kp{(K.sub.a +H.sup.+ !)/K.sub.a } 
where K.sub.a is the acid dissociation constant for hydrogen peroxide. 
Formation of diacylperoxide--A set of experiments is completed to measure 
the rate of formation of a diacylperoxide RC(O)O.sub.2 C(O)R from a bleach 
activator RC(O)L in aqueous solution at pH=10.0 with constant ionic 
strength of 1M as adjusted by addition of NaCl. The temperature is 
maintained at 35.0.degree..+-.0.1.degree. C. and the solution is buffered 
with NaHCO.sub.3 +Na.sub.2 CO.sub.3. A solution of the activator 
(RC(O)L!=0.5 mM is reacted with varying concentrations of peracid under 
stopped-flow conditions and the rate of reaction is monitored optically. 
Reactions are run under pseudo first-order conditions in order to 
determine the bimolecular rate constant k.sub.D'. Each kinetic run is 
repeated at least five times with about eight different concentrations of 
peracid anion. All kinetic traces give satisfactory fits to a first-order 
kinetic rate law and a plot of the observed first-order rate constant 
versus total concentration of peracid is linear over the region 
investigated. The slope of this line is the derived second order rate 
constant k.sub.D'. The bimolecular rate constant for the formation of a 
diacylperoxide from peracid anion (k.sub.D) is calculated according to 
EQU k.sub.D =k.sub.D' {(K.sub.a +H.sup.+ !)/K.sub.a } 
where K.sub.a is the acid dissociation constant for the peracid 
RC(O)O.sub.2 H. One skilled in the art will realize that the pK.sub.a 
values for peracids fall into a rather narrow range from about 7 to about 
8.5 and that at pH=10.0, when K.sub.a .gtoreq. about 10.sup.-8, {(K.sub.a 
+H.sup.+ !)/K.sub.a }.congruent.1and k.sub.D .congruent.k.sub.D'. 
Test for Low pH Perhydrolysis Efficiency--This method is applicable as a 
test for screening any bleach activators RC(O)L (not intending to be 
limiting of any specific performance-enhanced bleach activator structure 
herein) by confirmation of the formation of peracid analyte RC(O)O.sub.2 
H. The minimum standard for low pH perhydrolysis efficiency (LPE) is a 
coefficient, as defined below, .gtoreq.0.15 within 10 minutes when tested 
under the conditions specified below. 
Test Protocol--Distilled, deionized water (495 mL; adjusted to pH 7.5 with 
NaH2PO.sub.4 and Na.sub.2 HPO.sub.4) is added to a 1000 mL beaker and 
heated to 40.degree..+-.1.degree. C. Three hundred seventy-five (375) mg 
of 30% concentration hydrogen peroxide is added to the beaker and the 
mixture is stirred for two minutes before a 5 mL solution containing 100 
mg of activator (predissolved in 5 mL of an organic solvent (e.g. methanol 
or dimethylformamide)) is added. The initial data point is taken 1 minute 
thereafter. A second sample is removed at 10 minutes. Sample aliquots (2 
mL) are examined via analytical HPLC for the quantitative determination of 
peracid RC(O)O.sub.2 H. 
Sample aliquots are individually mixed with 2 mL of a pre-chilled 5.degree. 
C. solution of acetonitrile/acetic acid (86/14) and placed in temperature 
controlled 5.degree. C. autosampler for subsequent injection onto the HPLC 
column. 
High performance liquid chromatography of the authentic peracid under a 
given set of conditions establishes the characteristic retention time 
(t.sub.R) for the analyte. Conditions for the chromatography will vary 
depending on the peracid of interest and should be chosen so as to allow 
baseline separation of the peracid from other analytes. A standard 
calibration curve (peak area vs. concentration) is constructed using the 
peracid of interest. The analyte peak area of the 10 minute sample from 
the above described test is thereby converted to ppm peracid generated for 
determination of the quantity LPE. A bleach activator is considered 
acceptable when a value of the low pH perhydrolysis efficiency 
coefficient, LPE=(ppm of peracid generated)/(theoretical ppm 
peracid)!.gtoreq.0.15 is achieved within ten minutes under the specified 
test conditions. 
To note, by comparison with 4,5-saturated cyclic amidine embodiments of the 
instant bleach activators, known closely related chemical compounds 
wherein the 4,5 position is unsaturated have surprisingly greater rates of 
hydrolysis. Specifically, acetyl imidazole has k.sub.H greater than 
10.0M.sup.-1 s.sup.31 1 : accordingly this invention does not encompass 
imidazole as a leaving group. 
Source of hydrogen peroxide--A source of hydrogen peroxide herein is any 
convenient compound or mixture which under consumer use conditions 
provides an effective amount of hydrogen peroxide. Levels in general may 
vary widely and are typically from about 0.5% to about 70%, more typically 
from about 0.5%. to about 25%, by weight of the bleaching compositions 
herein. 
The source of hydrogen peroxide used herein can be any convenient source, 
including hydrogen peroxide itself. For example, perborate, e.g., sodium 
perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium 
carbonate peroxyhydrate or equivalent percarbonate salts, sodium 
pyrophosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide can be 
used herein. Mixtures of any convenient hydrogen peroxide sources can also 
be used. 
A preferred percarbonate bleach comprises dry particles having an average 
particle size in the range from about 500 micrometers to about 1,000 
micrometers, not more than about 10% by weight of said particles being 
smaller than about 200 micrometers and not more than about 10% by weight 
of said particles being larger than about 1,250 micrometers. Optionally, 
the percarbonate can be coated with silicate, borate or water-soluble 
surfactants. Percarbonate is available from various commercial sources 
such as FMC, Solvay and Tokai Denka. 
Detersive Surfactants--Surfactants are usefull herein for their usual 
cleaning power and are generally used at the usual detergent-useful 
levels. 
Nonlimiting examples of surfactants useful herein fall into two classes: 
those which can act as a pH-reducing nonsoap detersive ingredient, and 
those which can not. In the former of these two classes are the 
conventional C.sub.11 -C.sub.18 alkylbenzene sulfonates ("LAS") and 
primary, branched-chain and random C.sub.10 -C.sub.20 alkyl sulfates 
("AS"), the C.sub.10 -C.sub.18 secondary (2,3) alkyl sulfates of the 
formula CH.sub.3 (CH.sub.2).sub.x (CHOSO.sub.3 --M.sup.+)CH.sub.3 and 
CH.sub.3 (CH.sub.2).sub.y (CHOSO.sub.3 --M.sup.+)CH.sub.2 CH.sub.3 where x 
and (y+1) are integers of at least about 7, preferably at least about 9, 
and M is a water-solubilizing cation, especially sodium, unsaturated 
sulfates such as oleyl sulfate, the C.sub.10 -C.sub.18 alkyl alkoxy 
sulfates ("AE.sub.x S"; especially EO 1-7 ethoxy sulfates), C.sub.10 
-C.sub.18 alkyl alkoxy carboxylates (especially the EO 1-5 
ethoxycarboxylates), and C.sub.12 -C.sub.18 alpha-sulfonated fatty acid 
esters. If desired, the conventional amphoteric surfactants such as the 
C.sub.12 -C.sub.18 betaines and sulfobetaines ("sultaines"), C.sub.10 
-C.sub.18 amine oxides, and the like, can also be included in the overall 
compositions. 
Optional surfactants, i.e., those in the second of the above-identified 
classes, which cannot normally serve for pH reduction herein, include the 
C.sub.1O -C.sub.18 glycerol ethers, the C.sub.1O -C.sub.18 alkyl 
polyglycosides and their corresponding sulfated polyglycosides; C.sub.12 
-C.sub.18 alkyl ethoxylates ("AE") including the so-called narrow peaked 
alkyl ethoxylates and C.sub.6 -C.sub.12 alkyl phenol alkoxylates 
(especially ethoxylates and mixed ethoxylate/propoxylates). 
Other preferred optional surfactants include the C.sub.10 -C.sub.18 N-alkyl 
polyhydroxy fatty acid amides can also be used. Typical examples include 
the C.sub.12 -C.sub.18 N-methylglucamides. See WO 9,206,154. Other 
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid 
amides, such as C.sub.12 -C.sub.18 N-(3-methoxypropyl) glucamide. The 
N-propyl through N-hexyl C.sub.12 -C.sub.18 glucamides can be used for low 
sudsing. 
Optionally, C.sub.8 -C.sub.20 conventional soaps may also be used. If high 
sudsing is desired, the branched-chain C.sub.10 -C.sub.16 soaps may be 
used. 
Mixtures of anionic and nonionic surfactants are especially useful. Other 
conventional useful surfactants are listed in standard texts. 
Adjunct Ingredients--While effective bleach-additives herein may comprise 
only the bleach activators of the invention, fully-formulated laundry 
compositions typically will also comprise other adjunct ingredients to 
improve or modify performance. Typical, non-limiting examples of such 
ingredients are disclosed hereinafter for the convenience of the 
formulator. 
Bleach catalysts--If desired, the bleaches can be catalyzed by means of a 
manganese compound. Such compounds are well known in the art and include, 
for example, the manganese-based catalysts disclosed in U.S. Pat. No. 
5,246,621, U.S. Pat. No. 5,244,594; U.S. Pat. No. 5,194,416; U.S. Pat. No. 
5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,272A1, 
544,440A2, and 544,490A1; Preferred examples of these catalysts include 
Mn.sup.IV.sub.2 (u-O).sub.3 
(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2 -(PF.sub.6).sub.2, 
Mn.sup.III.sub.2 (u-O).sub.1 (u-OAc).sub.2 
(1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2 (ClO.sub.4).sub.2, 
Mn.sup.IV.sub.4 (u-O).sub.6 (1,4,7-triazacyclononane).sub.4 
(ClO.sub.4).sub.4, Mn.sup.III- Mn.sup.IV.sub.4 -(u-O).sub.1 (u-OAc).sub.2 
-(1,4,7-trimethyl-1,4,7-triazacyclo-nonane).sub.2 -(ClO.sub.4).sub.3, 
Mn.sup.IV- (4,7-trimethyl-1,4,7-triazacyclo-nonane)-(OCH.sub.3).sub.3 
(PF.sub.6), and mixtures thereof. Other metal-based bleach catalysts 
include those disclosed in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 
5,114,611. The use of manganese with various complex ligands to enhance 
bleaching is also reported in the following U.S. Pat. Nos.: 4,728,455; 
5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 
5,227,084. 
Said manganese can be precomplexed with ethylenediaminedisuccinate or 
separately added, for example as a sulfate salt, with 
ethylenediaminedisuccinate. (See U.S. application Ser. No. 08/210,186, 
filed Mar. 17, 1994.) Other preferred transition metals in said 
transition-metal-containing bleach catalysts include iron or copper. 
Remarkably, preferred embodiments of the present invention in which the 
wash pH is in the range from about 6.5 to about 9.5 and there is present 
one of the above-indicated selected performance-enhanced bleach activators 
in combination with one of the above-indicated bleach catalysts, secure a 
particularly superior bleaching effect as compared with otherwise 
identical compositions in which conventional bleach activators such as 
TAED (see hereinbelow) are used in place of the performance-enhanced 
bleach activator. 
As a practical matter, and not by way of limitation, the bleaching 
compositions and processes herein can be adjusted to provide on the order 
of at least one part per ten million of the active bleach catalyst species 
in the aqueous washing liquor, and will preferably provide from about 0.1 
ppm to about 700 ppm, more preferably from about 1 ppm to about 50 ppm, of 
the catalyst species in the laundry liquor. 
Conventional Bleach Activators--"Conventional bleach activators" herein are 
any bleach activators which do not respect the above-identified provisions 
given in connection with the performance-boosting bleach activators. 
Numerous conventional bleach activators are known and are optionally 
included in the instant bleaching compositions. Various nonlimiting 
examples of such activators are disclosed in U.S. Pat. No. 4,915,854, 
issued Apr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. The 
nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) 
activators are typical, and mixtures thereof can also be used. See also 
U.S. Pat. No. 4,634,551 for other typical conventional bleach activators. 
Known amido-derived bleach activators are those of the formulae: R.sup.1 
N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L wherein 
R.sup.1 is an alkyl group containing from about 6 to about 12 carbon 
atoms, R.sup.2 is an alkylene containing from 1 to about 6 carbon atoms, 
R.sup.5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 
10 carbon atoms, and L is any suitable leaving group. Further illustration 
of optional, conventional bleach activators of the above formulae include 
(6-octanamido-caproyl)oxybenzenesulfonate, 
(6-nonanamidocaproyl)oxybenzenesul-fonate, 
(6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as 
described in U.S. Pat. No. 4,634,551. Another class of conventional bleach 
activators comprises the benzoxazin-type activators disclosed by Hodge et 
al in U.S. Pat. No. 4,966,723, issued Oct. 30, 1990. Still another class 
of conventional bleach activators includes those acyl lactam activators 
which do not provide the benefits and criticalities described herein. 
Examples of optional lactam activators include octanoyl caprolactam, 
3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl 
caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl 
valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. 
Bleaching agents other than hydrogen peroxide sources are also known in the 
art and can be utilized herein as adjunct ingredients. One type of 
non-oxygen bleaching agent of particular interest includes photoactivated 
bleaching agents such as the sulfonated zinc and/or aluminum 
phthalocyanines. See U.S. Pat. No. 4,033,718, issued Jul. 5, 1977 to 
Holcombe et al. If used, detergent compositions will typically contain 
from about 0.025% to about 1.25%, by weight, of such bleaches, especially 
sulfonated zinc phthalocyanine. 
Organic Peroxides, especially Diacyl Peroxides--are extensively illustrated 
in Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley 
and Sons, 1982 at pages 27-90 and especially at pages 63-72, all 
incorporated herein by reference. Suitable organic peroxides, especially 
diacyl peroxides, are further illustrated in "Initiators for Polymer 
Production", Akzo Chemicals Inc., Product Catalog, Bulletin No. 88-57, 
incorporated by reference. Preferred diacyl peroxides herein whether in 
pure or formulated form for granule, powder or tablet forms of the 
bleaching compositions constitute solids at 25.degree. C. e.g., CADET.RTM. 
BPO 78 powder form of dibenzoyl peroxide, from Akzo. Highly preferred 
organic peroxides, particularly the diacyl peroxides, for such bleaching 
compositions have melting points above 40.degree. C., preferably above 
50.degree. C. Additionally, preferred are the organic peroxides with 
SADT's (as defined in the foregoing Akzo publication) of 35.degree. C. or 
higher, more preferably 70.degree. C. or higher. Nonlimiting examples of 
diacyl peroxides useful herein include dibenzoyl peroxide, lauroyl 
peroxide, and dicumyl peroxide. Dibenzoyl peroxide is preferred. In some 
instances, diacyl peroxides are available in the trade which contain oily 
substances such as dioctyl phthalate. In general, particularly for 
automatic dishwashing applications, it is preferred to use diacyl 
peroxides which are substantially free from oily phthalates since these 
can form smears on dishes and glassware. 
Quaternary Substituted Bleach Activators--The present compositions can 
optionally further comprise conventional, known quaternary substituted 
bleach activators (QSBA). QSBA's are further illustrated in U.S. Pat. No. 
4,539,130, Sep. 3, 1985 and U.S. Pat. No. 4,283,301. British Pat. 
1,382,594, published Feb. 5, 1975, discloses a class of QSBA's optionally 
suitable for use herein. U.S. Pat. No. 4,818,426 issued Apr. 4., 1989 
discloses another class of QSBA's. Also see U.S. Pat. No. 5,093,022 issued 
Mar. 3, 1992 and U.S. Pat. No. 4,904,406, issued Feb. 27, 1990. 
Additionally, QSBA's are described in EP 552,812 A1 published Jul. 28, 
1993, and in EP 540,090 A2, published May 5, 1993. 
Builders--Detergent builders can optionally be included in the compositions 
herein to assist in controlling mineral hardness. Inorganic as well as 
organic builders can be used. Builders are typically used in fabric 
laundering compositions to assist in the removal of particulate soils. 
The level of builder can vary widely depending upon the end use of the 
composition and its desired physical form. When present, the compositions 
will typically comprise at least about 1% builder. High performance 
compositions typically comprise from about 10% to about 80%, more 
typically from about 15% to about 50% by weight, of the detergent builder. 
Lower or higher levels of builder, however, are not excluded. 
Inorganic or P-containing detergent builders include, but are not limited 
to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates 
(exemplified by the tripolyphosphates, pyrophosphates, and glassy 
polymeric meta-phosphates), phosphonates, phytic acid, silicates, 
carbonates (including bicarbonates and sesquicarbonates), sulphates, and 
aluminosilicates. However, non-phosphate builders are required in some 
locales. Importantly, the compositions herein function surprisingly well 
even in the presence of the so-called "weak" builders (as compared with 
phosphates) such as citrate, or in the so-called "underbuilt" situation 
that may occur with zeolite or layered silicate builders. See U.S. Pat. 
No. 4,605,509 for examples of preferred aluminosilicates. 
Examples of silicate builders are the alkali metal silicates, particularly 
those having a SiO.sub.2 :Na.sub.2 O ratio in the range 1.6:1 to 3.2:1 and 
layered silicates, such as the layered sodium silicates described in U.S. 
Pat. No. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6.RTM. is a 
crystalline layered silicate marketed by Hoechst (commonly abbreviated 
herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder 
does not contain aluminum. NaSKS-6 is the .delta.-Na.sub.2 SiO.sub.5 
morphology form of layered silicate and can be prepared by methods such as 
those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a 
highly preferred layered silicate for use herein, but other such layered 
silicates, such as those having the general formula NaMSi.sub.x O.sub.2x+1 
yH.sub.2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, 
preferably 2, and y is a number from 0 to 20, preferably 0 can be used 
herein. Various other layered silicates from Hoechst include NaSKS-5, 
NaSKS-7 and NaSKS-11, as the .alpha.-, .beta.- and .gamma.- forms. Other 
silicates may also be useful, such as for example magnesium silicate, 
which can serve as a crispening agent in granular formulations, as a 
stabilizing agent for oxygen bleaches, and as a component of suds control 
systems. 
Examples of carbonate builders are the alkaline earth and alkali metal 
carbonates as disclosed in German Patent Application No. 2,321,001 
published on Nov.15, 1973. Various grades and types of sodium carbonate 
and sodium sesquicarbonate may be used, certain of which are particularly 
useful as carriers for other ingredients, especially detersive 
surfactants. 
Aluminosilicate builders are useful in the present invention. 
Aluminosilicate builders are of great importance in most currently 
marketed heavy duty granular detergent compositions, and can also be a 
significant builder ingredient in liquid detergent formulations. 
Aluminosilicate builders include those having the empirical formula: 
M.sub.z (zAlO.sub.2).sub.y !.xH.sub.2 O wherein z and y are integers of 
at least 6, the molar ratio of z to y is in the range from 1.0 to about 
0.5, and x is an integer from about 15 to about 264. 
Useful aluminosilicate ion exchange materials are commercially available. 
These aluminosilicates can be crystalline or amorphous in structure and 
can be naturally-occurring aluminosilicates or synthetically derived. A 
method for producing aluminosilicate ion exchange materials is disclosed 
in U.S. Pat. No. 3,985,669, Krummel, et al, issued Oct. 12, 1976. 
Preferred synthetic crystalline aluminosilicate ion exchange materials 
useful herein are available under the designations Zeolite A, Zeolite P 
(B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the 
crystalline aluminosilicate ion exchange material has the formula: 
Na.sub.12 (AlO.sub.2).sub.12 (SiO.sub.2).sub.12 !.xH.sub.2 O wherein x is 
from about 20 to about 30, especially about 27. This material is known as 
Zeolite A. Dehydrated zeolites (x=0 -10) may also be used herein. 
Preferably, the aluminosilicate has a particle size of about 0.1-10 
microns in diameter. As with other builders such as carbonates, it may be 
desirable to use zeolites in any physical or morphological form adapted to 
promote surfactant carrier function, and appropriate particle sizes may be 
freely selected by the formulator. 
Organic detergent builders suitable for the purposes of the present 
invention include, but are not restricted to, a wide variety of 
polycarboxylate compounds. As used herein, "polycarboxylate" refers to 
compounds having a plurality of carboxylate groups, preferably at least 3 
carboxylates. Polycarboxylate builder can generally be added to the 
composition in acid form, but can also be added in the form of a 
neutralized salt or "overbased". When utilized in salt form, alkali 
metals, such as sodium, potassium, and lithium, or alkanolammonium salts 
are preferred. 
Included among the polycarboxylate builders are a variety of categories of 
useful materials. One important category of polycarboxylate builders 
encompasses the ether polycarboxylates, including oxydisuccinate, as 
disclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, and 
Lamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also 
"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, on 
May 5, 1987. Suitable ether polycarboxylates also include cyclic 
compounds, particularly alicyclic compounds, such as those described in 
U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. 
Other useful detergency builders include the ether hydroxypolycarboxylates, 
copolymers of maleic anhydride with ethylene or vinyl methyl ether, 
1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and 
carboxymethyloxysuccinic acid, the various alkali metal, ammonium and 
substituted ammonium salts of polyacetic acids such as 
ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as 
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, 
polymaleic acid, benzene 1,3,5-tricarboxylic acid, 
carboxymethyloxysuccinic acid, and soluble salts thereof. 
Citrate builders, e.g., citric acid and soluble salts thereof (particularly 
sodium salt), are polycarboxylate builders of particular importance for 
heavy duty laundry detergent formulations due to their availability from 
renewable resources and their biodegradability. Citrates can also be used 
in combination with zeolite and/or layered silicate builders. 
Oxydisuccinates are also especially useful in such compositions and 
combinations. 
Also suitable in the detergent compositions of the present invention are 
the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds 
disclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Useful 
succinic acid builders include the C.sub.5 -C.sub.20 alkyl and alkenyl 
succinic acids and salts thereof. A particularly preferred compound of 
this type is dodecenylsuccinic acid. Specific examples of succinate 
builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 
2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. 
Laurylsuccinates are the preferred builders of this group, and are 
described in European Patent Application 86200690.5/0,200,263, published 
Nov. 5, 1986. 
Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226, 
Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No. 3,308,067, 
Diehl, issued Mar. 7, 1967. See also U.S. Pat. No. 3,723,322. 
Fatty acids, e.g., C.sub.12 -C.sub.18 monocarboxylic acids, can also be 
incorporated into the compositions alone, or in combination with the 
aforesaid builders, especially citrate and/or the succinate builders, to 
provide additional builder activity. Such use of fatty acids will 
generally result in a diminution of sudsing, which should be taken into 
account by the formulator. 
In situations where phosphorus-based builders can be used, and especially 
in the formulation of bars used for hand-laundering operations, the 
various alkali metal phosphates such as the well-known sodium 
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be 
used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and 
other known phosphonates (see, for example, U.S. Pat. Nos. 3,159,581; 
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used. 
Chelating Agents--The compositions herein may also optionally contain one 
or more iron and/or manganese and/or copper chelating agents, e.g., 
diethylenetraminepenta acetic acid (DTPA). More generally, chelating 
agents suitable for use herein can be selected from the group consisting 
of aminocarboxylates, aminophosphonates, polyfunctionally-substituted 
aromatic chelating agents and mixtures thereof. Without intending to be 
bound by theory, it is believed that the benefit of these materials is due 
in part to their exceptional ability to remove iron and manganese ions 
from washing solutions by formation of soluble chelates; other benefits 
include inorganic film or scale prevention. Other suitable chelating 
agents for use herein are the commercial DEQUEST.RTM. series, and chelants 
from Monsanto, DuPont, and Nalco, Inc. Aminocarboxylates useful as 
optional chelating agents include ethylenediaminetetracetates, 
N-hydroxyethylethylene-diaminetriacetates, nitrilotriacetates, 
ethylenediamine tetraproprionates, triethylene-tetraaminehexacetates, 
diethylenetriamine-pentaacetates, and ethanoldiglycines, alkali metal, 
ammonium, and substituted ammonium salts therein and mixtures therein. 
Aminophosphonates are also suitable for use as chelating agents in the 
compositions of the invention when at least low levels of total phosphorus 
are permitted in detergent compositions, and include 
ethylenediaminetetrakis (methylenephosphonates). Preferably, these 
aminophosphonates do not contain alkyl or alkenyl groups with more than 
about 6 carbon atoms. 
Polyfunctionally-substituted aromatic chelating agents are also useful in 
the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21, 1974, 
to Connor et al. Preferred compounds of this type in acid form are 
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. 
A highly preferred biodegradable chelator for use herein is ethylenediamine 
disuccinate ("EDDS"), especially (but not limited to) the S,S! isomer as 
described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and 
Perkins. The trisodium salt is preferred though other forms, such as 
magnesium salts, may also be useful. 
If utilized, these chelating agents or transition-metal-selective 
sequestrants will preferably comprise from about 0.001% to about 10%, more 
preferably from about 0.05% to about 1% by weight of the bleaching 
detergent compositions herein. 
Enzymes--Enzymes can be included in the formulations herein for a wide 
variety of fabric laundering or other cleaning purposes, including removal 
of protein-based, carbohydrate-based, or triglyceride-based stains, for 
example, and for the prevention of refugee dye transfer, and for fabric 
restoration. The enzymes to be incorporated include proteases, amylases, 
lipases, cellulases, and peroxidases, as well as mixtures thereof. Other 
types of enzymes may also be included. They may be of any suitable origin, 
such as vegetable, animal, bacterial, fungal and yeast origin. However, 
their choice is governed by several factors such as pH-activity and/or 
stability optima, thermostability, stability versus active detergents, 
builders, etc.. In this respect bacterial or fungal enzymes are preferred, 
such as bacterial amylases and proteases, and fungal cellulases. 
Enzymes are normally incorporated at levels sufficient to provide up to 
about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of 
active enzyme per gram of the composition. Stated otherwise, the 
compositions herein will typically comprise from about 0.001% to about 5%, 
preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease 
enzymes are usually present in such commercial preparations at levels 
sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per 
gram of composition. 
Suitable examples of proteases are the subtilisins which are obtained from 
particular strains of B. subtilis and B. licheniformis. Another suitable 
protease is obtained from a strain of Bacillus, having maximum activity 
throughout the pH range of 8-12, developed and sold by Novo Industries A/S 
as ESPERASE.RTM.. The preparation of this enzyme and analogous enzymes is 
described in British Patent Specification No. 1,243,784 of Novo. 
Proteolytic enzymes suitable for removing protein-based stains that are 
commercially available include those sold under the tradenames 
ALCALASE.RTM. and SAVINASE.RTM. by Novo Industries A/S (Denmark) and 
MAXATASE.RTM. by International Bio-Synthetics, Inc. (The Netherlands). 
Other proteases include Protease A (see European Patent Application 
130,756, published Jan. 9, 1985) and Protease B (see European Patent 
Application Serial No. 87303761.8, filed Apr. 28, 1987, and European 
Patent Application 130,756, Bott et al, published Jan. 9, 1985). 
An especially preferred protease, referred to as "Protease D" is a carbonyl 
hydrolase variant having an amino acid sequence not found in nature, which 
is derived from a precursor carbonyl hydrolase by substituting a different 
amino acid for a plurality of amino acid residues at a position in said 
carbonyl hydrolase equivalent to position +76 in combination with one or 
more amino acid residue positions equivalent to those selected from the 
group consisting of +99, +101, +103, +107 and +123 in Bacillus 
amyloliquefaciens sbtilisin as described in the patent applications of A. 
Baeck, C. K. Ghosh, P. P. Greycar, R. R. Bott and L. J. Wilson, entitled 
"Protease-Containing Cleaning Compositions" having U.S. Ser. No. 
08/136,797 (P&G Case 5040), and "Bleaching Compositions Comprising 
Protease Enzymes" having U.S. Ser. No. 08/136,626. 
Amylases include, for example, .alpha.-amylases described in British Patent 
Specification No. 1,296,839 (Novo), RAPIDASE.RTM., International 
Bio-Synthetics, Inc. and TERMAMYL.RTM., Novo Industries. 
Cellulases usable in the present invention include both bacterial or fungal 
cellulases. Preferably, they will have a pH optimum of between 5 and 9.5. 
Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307, Barbesgoard 
et al, issued Mar. 6, 1984, which discloses fungal cellulase produced from 
Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing 
fungus belonging to the genus Aeromonas, and cellulase extracted from the 
hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable 
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and 
DE-OS-2.247.832. CAREZYME.RTM. (Novo) is especially useful. 
Suitable lipase enzymes for detergent use include those produced by 
microorganisms of the Pseudomonas group, such as Pseudomonas stuizeri ATCC 
19.154, as disclosed in British Patent 1,372,034. See also lipases in 
Japanese Patent Application 53,20487, laid open to public inspection on 
Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. 
Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter 
referred to as "Amano-P." Other commercial lipases include Amano-CES, 
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. 
lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, 
Japan; and further Chromobacter viscosum lipases from U.S. Biochemical 
Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex 
Pseudomonas gladioli. The LIPOLASE.RTM. enzyme derived from Humicola 
lanuginosa and commercially available from Novo (see also EPO 341,947) is 
a preferred lipase for use herein. 
Peroxidase enzymes can be used in combination with oxygen sources, e.g., 
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used 
for "solution bleaching," i.e. to prevent transfer of dyes or pigments 
removed from substrates during wash operations to other substrates in the 
wash solution. Peroxidase enzymes are known in the art, and include, for 
example, horseradish peroxidase, ligninase, and haloperoxidase such as 
chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions 
are disclosed, for example, in PCT International Application WO 89/099813, 
published Oct. 19, 1989, by O. Kirk, assigned to Novo Industries A/S. 
A wide range of enzyme materials and means for their incorporation into 
synthetic detergent compositions are also disclosed in U.S. Pat. No. 
3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are further 
disclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978, 
and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985. Enzyme 
materials useful for liquid detergent formulations, and their 
incorporation into such formulations, are disclosed in U.S. Pat. No. 
4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use in detergents 
can be stabilized by various techniques. Enzyme stabilization techniques 
are disclosed and exemplified in U.S. Pat. No. 3,600,319, issued Aug. 17, 
1971 to Gedge, et al, and European Patent Application Publication No. 0 
199 405, Application No. 86200586.5, published Oct. 29, 1986, Venegas. 
Enzyme stabilization systems are also described, for example, in U.S. Pat. 
No. 3,519,570. 
Polymeric Soil Release Agent--Any polymeric soil release agent known to 
those skilled in the art can optionally be employed in the compositions 
and processes of this invention. Polymeric soil release agents are 
characterized by having both hydrophilic segments, to hydrophilize the 
surface of hydrophobic fibers, such as polyester and nylon, and 
hydrophobic segments, to deposit upon hydrophobic fibers and remain 
adhered thereto through completion of washing and rinsing cycles and, 
thus, serve as an anchor for the hydrophilic segments. This can enable 
stains occurring subsequent to treatment with the soil release agent to be 
more easily cleaned in later washing procedures. 
The polymeric soil release agents useful herein especially include those 
soil release agents having: (a) one or more nonionic hydrophile components 
consisting essentially of (i) polyoxyethylene segments with a degree of 
polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene 
segments with a degree of polymerization of from 2 to 10, wherein said 
hydrophile segment does not encompass any oxypropylene unit unless it is 
bonded to adjacent moieties at each end by ether linkages, or (iii) a 
mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 
oxypropylene units wherein said mixture contains a sufficient amount of 
oxyethylene units such that the hydrophile component has hydrophilicity 
great enough to increase the hydrophilicity of conventional polyester 
synthetic fiber surfaces upon deposit of the soil release agent on such 
surface, said hydrophile segments preferably comprising at least about 25% 
oxyethylene units and more preferably, especially for such components 
having about 20 to 30 oxypropylene units, at least about 50% oxyethylene 
units; or (b) one or more hydrophobe components comprising (i) C.sub.3 
oxyalkylene terephthalate segments, wherein, if said hydrophobe components 
also comprise oxyethylene terephthalate, the ratio of oxyethylene 
terephthalate:C.sub.3 oxyalkylene terephthalate units is about 2:1 or 
lower, (ii) C.sub.4 -C.sub.6 alkylene or oxy C.sub.4 -C.sub.6 alkylene 
segments, or mixtures therein, (iii) poly (vinyl ester) segments, 
preferably polyvinyl acetate), having a degree of polymerization of at 
least 2, or (iv) C.sub.1 -C.sub.4 alkyl ether or C.sub.4 hydroxyalkyl 
ether substituents, or mixtures therein, wherein said substituents are 
present in the form of C.sub.1 -C.sub.4 alkyl ether or C.sub.4 
hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such 
cellulose derivatives are amphiphilic, whereby they have a sufficient 
level of C.sub.1 -C.sub.4 alkyl ether and/or C.sub.4 hydroxyalkyl ether 
units to deposit upon conventional polyester synthetic fiber surfaces and 
retain a sufficient level of hydroxyls, once adhered to such conventional 
synthetic fiber surface, to increase fiber surface hydrophilicity, or a 
combination of (a) and (b). 
Typically, the polyoxyethylene segments of (a)(i) will have a degree of 
polymerization of from about 200, although higher levels can be used, 
preferably from 3 to about 150, more preferably from 6 to about 100. 
Suitable oxy C.sub.4 -C.sub.6 alkylene hydrophobe segments include, but 
are not limited to, end-caps of polymeric soil release agents such as 
MO.sub.3 S(CH.sub.2).sub.n OCH.sub.2 CH.sub.2 O--, where M is sodium and n 
is an integer from 4-6, as disclosed in U.S. Pat. No. 4,721,580, issued 
Jan. 26, 1988 to Gosselink. 
Polymeric soil release agents useful in the present invention also include 
cellulosic derivatives such as hydroxyether cellulosic polymers, 
copolymeric blocks of ethylene terephthalate or propylene terephthalate 
with polyethylene oxide or polypropylene oxide terephthalate, and the 
like. Such agents are commercially available and include hydroxyethers of 
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use 
herein also include those selected from the group consisting of C.sub.1 
-C.sub.4 alkyl and C.sub.4 hydroxyalkyl cellulose; see U.S. Pat. No. 
4,000,093, issued Dec. 28, 1976 to Nicol, et al. 
Soil release agents characterized by poly(vinyl ester) hydrophobe segments 
include graft copolymers of poly(vinyl ester), e.g., C.sub.1 -C.sub.6 
vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene 
oxide backbones, such as polyethylene oxide backbones. See European Patent 
Application 0 219 048, published Apr. 22, 1987 by Kud, et al. Commercially 
available soil release agents of this kind include the SOKALAN type of 
material, e.g., SOKALAN HP-22, available from BASF (West Germany). 
One type of preferred soil release agent is a copolymer having random 
blocks of ethylene terephthalate and polyethylene oxide (PEO) 
terephthalate. The molecular weight of this polymeric soil release agent 
is in the range of from about 25,000 to about 55,000. See U.S. Pat. No. 
3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 to 
Basadur issued Jul. 8, 1975. 
Another preferred polymeric soil release agent is a polyester with repeat 
units of ethylene terephthalate units containing 10-15% by weight of 
ethylene terephthalate units together with 90-80% by weight of 
polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol 
of average molecular weight 300-5,000. Examples of this polymer include 
the commercially available material ZELCON 5126 (from Dupont) and MILEASE 
T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to 
Gosselink. 
Another preferred polymeric soil release agent is a sulfonated product of a 
substantially linear ester oligomer comprised of an oligomeric ester 
backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal 
moieties covalently attached to the backbone. These soil release agents 
are described fully in U.S. Pat. No. 4,968,451, issued Nov. 6, 1990 to J. 
J. Scheibel and E. P. Gosselink. Other suitable polymeric soil release 
agents include the terephthalate polyesters of U.S. Pat. No. 4,711,730, 
issued Dec. 8, 1987 to Gosselink et al, the anionic end-capped oligomeric 
esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink, and 
the block polyester oligomeric compounds of U.S. Pat. No. 4,702,857, 
issued Oct. 27, 1987 to Gosselink. 
Preferred polymeric soil release agents also include the soil release 
agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado et 
al, which discloses anionic, especially sulfoaroyl, end-capped 
terephthalate esters. 
Still another preferred soil release agent is an oligomer with repeat units 
of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and 
oxy-1,2-propylene units. The repeat units form the backbone of the 
oligomer and are preferably terminated with modified isethionate end-caps. 
A particularly preferred soil release agent of this type comprises about 
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and 
oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and 
two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. These 
sulfo-end-capeed soil release agents also comprise from about 0.5% to 
about 20%, by weight of the oligomer, of a crystalline-reducing 
stabilizer, preferably selected from the group consisting of xylene 
sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof. 
If utilized, soil release agents will typically comprise from about 0.01% 
to about 10.0%, by weight, of the detergent compositions herein, typically 
from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%. 
Other Ingredients--Usual detersive ingredients can include one or more 
other detersive adjuncts or other materials for assisting or enhancing 
cleaning performance, treatment of the substrate to be cleaned, or to 
modify the aesthetics of the detergent composition. Usual detersive 
adjuncts of detergent compositions include the ingredients set forth in 
U.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which can also be 
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 ingredients, preferably from about 0.5% to 
about 10%), include other active ingredients such as dispersant polymers 
from BASF Corp. or Rohm & Haas; color speckles, anti-tarnish and/or 
anti-corrosion agents, dyes, fillers, optical brighteners, germicides, 
alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizing agents, 
perfumes, solubilizing agents, clay soil remolval/anti-redeposition 
agents, carriers, processing aids, pigments, solvents for liquid 
formulations, fabric softeners, static control agents, solid fillers for 
bar compositions, etc. Dye transfer inhibiting agents, including polyamine 
N-oxides such as polyvinylpyridine N-oxide can be used. 
Dye-transfer-inhibiting agents are further illustrated by 
polyvinylpyrrolidone and copolymers of N-vinyl imidazole and N-vinyl 
pyrrolidone. If high sudsing is desired, suds boosters such as the 
C.sub.10 -C.sub.16 alkanolamides can be incorporated into the 
compositions, typically at 1%-10% levels. The C.sub.10 -C.sub.14 
monoethanol and diethanol amides illustrate a typical class of such suds 
boosters. Use of such suds boosters with high sudsing adjunct surfactants 
such as the amine oxides, betaines and sultaines noted above is also 
advantageous. If desired, soluble magnesium salts such as MgCl.sub.2, 
MgSO.sub.4 , and the like, can be added at levels of, typically, 0.1%-2%, 
to provide additional suds and to enhance grease removal performance. 
Brightener--Any optical brighteners or other brightening or whitening 
agents known in the art can be incorporated at levels typically from about 
0.05% to about 1.2%, by weight, into the detergent compositions herein. 
Commercial optical brighteners which may be useful in the present 
invention can be classified into subgroups, which include, but are not 
necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, 
carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- 
and 6-membered-ring heterocycles, and other miscellaneous agents. Examples 
of such brighteners are disclosed in "The Production and Application of 
Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & 
Sons, New York (1982). 
Specific examples of optical brighteners which are useful in the present 
compositions are those identified in U.S. Pat. No. 4,790,856, issued to 
Wixon on Dec. 13, 1988. These brighteners include the PHORWHITE series of 
brighteners from Verona. Other brighteners disclosed in this reference 
include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from 
Ciba-Geigy; Artic White CC and Artic White CWD, available from 
Hilton-Davis, located in Italy; the 
2-(4-stryl-phenyl)-2H-napthol1,2-d!triazoles; 4,4'-bis- 
(1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(stryl)bisphenyls; and the 
aminocoumarins. Specific examples of these brighteners include 
4-methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene; 
1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 
2-stryl-napth-1,2-d!oxazole; and 2-(stilbene-4-yl)-2H-naphtho- 
1,2-d!triazole. See also U.S. Pat. No. 3,646,015, issued Feb. 29, 1972 to 
Hamilton. Anionic brighteners are preferred herein. 
Various detersive ingredients employed in the present compositions 
optionally can be further stabilized by absorbing said ingredients onto a 
porous hydrophobic substrate, then coating said substrate with a 
hydrophobic coating. Preferably, the detersive ingredient is admixed with 
a surfactant before being absorbed into the porous substrate. In use, the 
detersive ingredient is released from the substrate into the aqueous 
washing liquor, where it performs its intended detersive function. 
To illustrate this technique in more detail, a porous hydrophobic silica 
(trademark SIPERNAT.RTM. D10, Degussa) is admixed with a proteolytic 
enzyme solution containing 3%-5% of C.sub.13-15 ethoxylated alcohol (EO 7) 
nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X 
the weight of silica. The resulting powder is dispersed with stirring in 
silicone oil (various silicone oil viscosities in the range of 500-12,500 
can be used). The resulting silicone oil dispersion is emulsified or 
otherwise added to the final detergent matrix. By this means, ingredients 
such as the aforementioned enzymes, bleaches, bleach activators, bleach 
catalysts, photoactivators, dyes, fluorescers, fabric conditioners and 
hydrolyzable surfactants can be "protected" for use in detergents, 
including liquid laundry detergent compositions. 
Bleaching compositions in granular form typically limit water content, for 
example to less than about 12% free water, for best storage stability. 
Storage stability of bleaching detergent compositions can be further 
enhanced by limiting the content in the compositions of adventitious 
redox-active substances such as rust and other traces of transition metals 
in undesirable form. Certain bleaching compositions may moreover be 
limited in their total halide ion content, or may have any particular 
halide, e.g., bromide, substantially absent. Bleach stabilizers such as 
stannates can be added for improved stability and liquid formulations may 
be substantially nonaqueous if desired. 
The following examples illustrate the bleach activators of the invention 
and bleaching detergent compositions which can be prepared using the 
bleach activators, but are not intended to be limiting thereof. All 
material in Examples I-XXX satisfy the functional limitations herein.

EXAMPLE I 
N-(4-methylsulfonyl)benzoyl! caprolactam: 
All glassware is dried thoroughly, and the reaction kept under an inert 
atmosphere (argon) at all times. 
With stirring, 5.0 g (25.0 mmol) of (4-methylsulfonyl)benzoic acid 
(Aldrich) and 5.5 mL (75.0 mmol) of thionyl chloride (Aldrich, d=1.631 
g/mol) are added to 100 mL tetrahydrofuran (THF--Aldrich, BPLC grade) in a 
3-neck round bottom flask equipped with a reflux condenser, addition 
funnel, and magnetic stirrer. The resulting reaction mixture is heated to 
reflux and stirred for 16 h. After cooling to room temperature, the 
solvent and excess thionyl chloride are removed by evaporation under 
reduced pressure. Recrystallization of the solid residue from toluene 
followed by drying under high vacuum yields pure (4-methylsulfonyl)benzoyl 
chloride as a white, crystalline solid. 
In a subsequent reaction, 2.33 g (20.6 mmol) of caprolactam (Aldrich) and 
2.30 g (22.7 mmol) of triethylamine (Aldrich, d=0.726 g/mol) are added to 
50 mL THF (Aldrich, HPLC grade) in a 3-neck round bottom flask equipped 
with a reflux condenser, addition funnel, and magnetic stirrer. Addition 
of a solution of 4.50 g (20.6 mmol) of the (4-methylsulfonyl)-benzoyl 
chloride in 50 mL THF proceeds dropwise over a period of 30 min, and the 
resulting reaction mixture is heated to reflux and stirred for 16 h. Upon 
cooling to room temperature, the THF is removed by evaporation under 
reduced pressure. The solid residue is redissolved in chloroform, and 
extracted several times with D.I. water. The organic layer is dried over 
Na.sub.2 SO.sub.4, filtered, concentrated by removal of solvent, and 
poured into hexane to precipitate the product. The precipitate is 
collected by suction filtration, rinsed with hexane, and dried under 
vacuum to yield N-(4-methylsulfonyl)benzoyl! caprolactam as a white, 
crystalline solid. 
EXAMPLE II 
N-(4-methylsulfonyl)benzoyl!valerolactam: 
Synthesized as for N-(4-methylsulfonyl)benzoyl!caprolactam (Example I) 
using valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE III 
N-(4-ethylsulfonyl)benzoyl!caprolactam: 
The synthesis of N-(4-ethylsulfonyl)benzoyl!caprolactam proceeds as for N- 
(4-methylsulfonyl)benzoyl!caprolactam (Example I) using 
(4-ethylsulfonyl)benzoic acid in place of (4-methylsulfonyl)benzoic acid. 
The (4-ethylsulfonyl)benzoic acid can be synthesized from 2-chloropropionic 
acid and 4-(chlorosulfonyl)benzoic acid according to the procedure of 
Brown, R. W. J. Org. Chem. 1991, 56, 4974-4976. 
EXAMPLE IV 
N-(4-ethylsulfonyl)benzoyl!valerolactam: 
Synthesized as for N-(4-ethylsulfonyl)benzoyl!caprolactam (Example III) 
using valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE V 
N-(4-pentylsulfonyl)benzoyl!caprolactam: 
Synthesized as for N-(4-ethylsulfonyl)benzoyl!caprolactam (Example III) 
using 2-bromohexanoic acid (Aldrich) in place of 2-chloropropionic acid. 
EXAMPLE VI 
N-(4-pentylsulfonyl)benzoyl!valerolactam: 
Synthesized as for N-(4-pentylsulfonyl)benzoyl!caprolactam (Example V) 
using valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE VII 
N-(4-heptysulfonyl)benzoyl!caprolactam: 
Synthesized as for N-(4-ethylsulfonyl)benzoyl!caprolactam (Example III) 
using 2-bromooctanoic acid (Aldrich) in place of 2-chloropropionic acid. 
EXAMPLE VIII 
N-(4-heptylsulfonyl)benzoyl!valerolactam: 
Synthesized as for N-(4-heptylsulfonyl)benzoyl!caprolactam (Example VII) 
using valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE IX 
N-(2-furoyl)valerolactam: 
All glassware is dried thoroughly, and the reaction is kept under an inert 
atmosphere (argon) at all times. With stirring, 20.0 g (0.18 mol) of 
2-furoic acid (Aldrich) and 40.0 mL (0.53 mol) of thionyl chloride 
(Aldrich, d=1.631 g/mol) are added to 300 mL THF (Aldrich, HPLC grade) in 
a single-neck round bottom flask equipped with a reflux condenser and 
magnetic stirrer. The resulting reaction mire is heated to reflux and 
stirred for 16 h. After cooling to room temperature, the solvent and 
excess thionyl chloride are removed by evaporation under reduced pressure 
to yield 2-furoyl chloride. 
In a subsequent reaction, 9.2 g (92 mmol) of valerolactam (Aldrich) and 
14.1 mL (101 mmol) of triethylamine (Aldrich, d=0.726 g/mol) are added to 
150 mL THF (Aldrich, HPLC grade) in a 3-neck round bottom flask equipped 
with a reflux condenser, addition funnel, and magnetic stirrer. Addition 
of a solution of 12.0 g (92 mmol) of the 2-furoyl chloride in 150 mL THF 
proceeds dropwise over a period of 30 min, and the resulting reaction 
mixture is heated to reflux and stirred for 16 h. Upon cooling to room 
temperature, the THF is removed by evaporation under reduced pressure. The 
solid residue is redissolved in methylene chloride, and extracted several 
times with 5% aqueous hydrochloric and then deionized water. The organic 
layer is dried over Na.sub.2 SO.sub.4, filtered, concentrated by removal 
of solvent, and poured into hexane to precipitate the product. The 
precipitate is collected by suction filtration, rinsed with hexane, and 
dried under vacuum to yield N-(2-furoyl)valerolactam as a white, 
crystalline solid. 
EXAMPLE X 
N-(2-furoyl)caprolactam: 
Synthesized as for N-(2-furoyl)valerolactam (Example IX) using caprolactam 
(Aldrich) in place of valerolactam. 
EXAMPLE XI 
N-(3-furoyl)caprolactam: 
Synthesized as for N-(2-furoyl)caprolactam (Example X) using 3-furoic acid 
in place of 2-furoic acid. 
EXAMPLE XII 
N-(3-furoyl)valerolactam: 
Synthesized as for N-(3-furoyl)caprolactam (Example XI) using valerolactam 
(Aldrich) in place of caprolactam. 
EXAMPLE XIII 
N-(5-nitro-2-furoyl)caprolactam: 
Synthesized as for N-(2-furoyl)caprolactam (Example XI) using 
5-nitro-2-furoic acid in place of 2-furoic acid. 
EXAMPLE XIV 
N-(5-nitro-2-furoyl)valerolactam: 
Synthesized as for N-(5-nitro-2-furoyl)caprolactam (Example XIII) using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XV 
N-(5-bromo-2-furoyl)caprolactam: 
Synthesized as for N-(2-furoyl)caprolactam (Example X) using 
5-bromo-2-furoic acid in place of 2-furoic acid. 
EXAMPLE XVI 
N-(5-bromo-2-furoyl)valerolactam: 
Synthesized as for N-(5-bromo-2-furoyl)caprolactam (Example XV) using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XVII 
N-(1-naphthoyl)caprolactam: 
Synthesized as for N-(2-furoyl)caprolactam (Example X) using 1-naphthoic 
acid in place of 2-furoic acid. 
EXAMPLE XVIII 
N-(1-naphthoyl)valerolactam: 
Synthesized as for N-(1-naphthoyl)caprolactam (Example XVII) using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XIX 
N-(3,5-dinitrobenzoyl)caprolactam: 
All glassware is dried thoroughly, and the reaction is kept under an inert 
atmosphere (argon) at all times. With stirring, 2.33 g (20.6 mmol) of 
caprolactam (Aldrich) and 2.30 g (22.7 mmol) of triethylamine (Aldrich, 
d=0.726 g/mol) are added to 100 mL toluene (Aldrich) in a 3-neck round 
bottom flask equipped with a reflux condenser, addition funnel, and 
mechanical stirrer, to give a clear, pale yellow solution. Addition of a 
solution of 4.75 g (20.6 mmol) of 3,5-dinitrobenzoyl chloride (Aldrich) in 
100 mL toluene proceeds dropwise over a period of 30 min. The resulting 
reaction mixture is heated to reflux and stirred for 16 h. Upon cooling to 
room temperature, the reaction is filtered to remove the triethylamine 
hydrochloride, and poured into a separatory funnel. After dilution with 
300 mL of chloroform, the organic solution is extracted with 5% aq HCl, 5% 
aq NaOH, and finally D.I. water. The organic layer is dried over Na.sub.2 
SO4, filtered, and the solvent removed by evaporation under reduced 
pressure. Recrystallization of the crude product from toluene followed by 
drying under vacuum yields N-(3,5-dinitrobenzoyl)caprolactam as a light 
yellow, crystalline solid. 
EXAMPLE XX 
N-(3,5-dinitrobenzoyl)valerolactam: 
Synthesized as for N-(3,5-dinitrobenzoyl)caprolactam (Example XIX) using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XXI 
N-(3,5-dichlorobenzoyl)caprolactam: 
Synthesized as for N-(4-nitrobenzoyl)caprolactam (Example XXIII) using 
3,5-dichlorobenzoylchloride (Aldrich) in place of 4-nitrobenzoyl chloride. 
EXAMPLE XXII 
N-(3,5-dichlorobenzoyl)valerolactam: 
Synthesized as for N-(3,5-dichlorobenzoyl)caprolactam (Example XXI) using 
valerolactam (Aldrich) in place of caprolactam. 
Examples XXIII-XXX exemplify methods for synthesizing compounds generically 
disclosed in prior references. 
EXMPLE XXIII 
N-(4-nitrobenzoyl)caprolactam: 
All glassware is dried thoroughly, and the reaction is kept under an inert 
atmosphere (argon) at all times. With stirring, 43.0 g (0.38 mol) of 
caprolactam (Aldrich) and 58.2 mL (0.42 mol) of triethylamine (Aldrich, 
d=0.726 g/mol) is added to 150 mL THF (Aldrich, HPLC grade) in a 3-neck 
round bottom flask equipped with a reflux condenser, addition funnel, and 
mechanical stirrer, to give a clear, pale yellow solution. Addition of a 
solution of 70.5 g (0.38 mol) of 4-nitrobenzoyl chloride (Aldrich) in 100 
mL THF proceeds dropwise over a period of 1 h. The cloudy, dark yellow 
reaction mixture is heated to reflux and stirred for 16 h. 
Upon cooling to room temperature, the reaction is filtered to remove the 
triethylamine hydrochloride, and poured into a separatory funnel. After 
dilution with chloroform, the organic solution is extracted twice 5% aq 
HCl, twice with 5% aq NaOH, and finally once with neutral D.I. water. The 
organic layer is dried over Na.sub.2 SO.sub.4 or MgSO.sub.4, filtered, and 
the solvent removed by evaporation under reduced pressure. 
Recrystallization of the crude product from toluene followed by drying 
under vacuum yields N-(4-nitrobenzoyl)caprolactam as a light yellow, 
crystalline solid. 
EXAMPLE XXIV 
N-(4-nitrobenzoyl)valerolactam: 
Synthesized as for N-(4-nitrobenzoyl)caprolactam (Example XXIII using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XXV 
N-(3-nitrobenzoyl)caprolactam: 
Synthesized as for N-(4-nitrobenzoyl)caprolactam (Example XXIII) using 
3-nitrobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride. 
EXAMPLE XXVI 
N-(3-nitrobenzoyl)valerolactam: 
Synthesized as for N-(3-nitrobenzoyl)caprolactam (Example XXV) using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XXVII 
N-(3-chlorobenzoyl)caprolactam: 
Synthesized as for N-(4-nitrobenzoyl)caprolactam (Example XXIII using 
3-chlorobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride. 
EXAMPLE XXVIII 
N-(3-chlorobenzoyl)valerolactam: 
Synthesized as for N-(3-chloroobenzoyl)caprolactam (Example XXVII using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XXIX 
N-(4-chlorobenzoyl)caprolactam: 
Synthesized as for N-(4-nitrobenzoyl)caprolactam (Example XXIII) using 
4-chlorobenzoylchloride (Aldrich) in place of 4-nitrobenzoyl chloride. 
EXAMPLE XXX 
N-(4-chlorobenzoyl)valerolactam: 
Synthesized as for N-(4-chlorobenzoyl)caprolactam (Example XXIX using 
valerolactam (Aldrich) in place of caprolactam. 
EXAMPLE XXXI 
Bleaching detergent compositions having the form of granular laundry 
detergents are exemplified by the following formulations. 
______________________________________ 
A B C D E 
______________________________________ 
Bleach Activator* 
2.30 2.30 3.00 4.60 2.30 
Sodium Percarbonate 
5.30 0.00 0.00 12.00 0.00 
Sodium Perborate 
0.00 5.30 9.00 0.00 5.30 
Monohydrate 
Linear Alkylbenzene- 
12.00 0.00 12.00 0.00 21.00 
sulfonate 
C45AE0.6S 0.00 15.00 0.00 15.00 0.00 
C2 Dimethylamine 
0.00 2.00 0.00 2.00 0.00 
N-Oxide 
C12 Coco Amidopropyl 
1.50 0.00 1.50 0.00 0.00 
Betaine 
Palm N- Methyl 
1.70 2.00 1.70 2.00 0.00 
Glucamide 
C12 Dimethylhydroxy- 
1.50 0.00 1.50 0.00 0.00 
ethylammonium Chloride 
AE23-6.5T 2.50 3.50 2.50 3.50 1.00 
C25E3S 4.00 0.00 4.00 0.00 0.00 
Conventional Activator 
0.00 0.00 0.00 0.00 0.00 
(NOBS) 
Conventional Activator 
0.00 0.00 0.00 0.00 0.00 
(TAED) 
Sodium Tripoly- 
25.00 25.00 15.00 15.00 25.00 
phosphate 
Zeolite A 0.00 0.00 0.00 0.00 0.00 
Acrylic Acid/Maleic 
0.00 0.00 0.00 0.00 1.00 
Acid Copolymer 
Polyacrylic Acid, 
3.00 3.00 3.00 3.00 0.00 
partially neutralized 
Soil Release Agent 
0.00 0.00 0.50 0.40 0.00 
Carboxymethylcellulose 
0.40 0.40 0.40 0.40 0.40 
Sodium Carbonate 
2.00 2.00 2.00 0.00 8.00 
Sodium Silicate 
3.00 3.00 3.00 3.00 6.00 
Sodium Bicarbonate 
5.00 5.00 5.00 5.00 5.00 
Savinase (4T) 
1.00 1.00 1.00 1.00 0.60 
Termamyl (60T) 
0.40 0.40 0.40 0.40 0.40 
Lipolase (100T) 
0.12 0.12 0.12 0.12 0.12 
Carezyme (5T) 
0.15 0.15 0.15 0.15 0.15 
Diethylenetriaminepenta 
1.60 1.60 1.60 1.60 0.40 
(methylenephosphonic 
Acid) 
Brightener 0.20 0.20 0.20 0.05 0.20 
Sulfonated Zinc 
0.50 0.00 0.25 0.00 0.00 
Phthalocyanine 
Photobleach 
MgSO4 2.20 2.20 2.20 2.20 0.64 
Na2SO4 balance balance balance 
balance 
balance 
______________________________________ 
Any of the above compositions is used to launder fabrics at a concentration 
of 3500 ppm in water, 25.degree. C., and a 15:1 water:cloth ratio. The 
typical pH is about 9.5 but can be can be adjusted by altering the 
proportion of acid to Na- salt form of alkylbenzenesulfonate. Results are 
excellent, particularly with respect to bleaching as compared with 
otherwise identical compositions in which TAED, NOBS or benzoylcaprolactam 
are used at equal weight as a complete replacement for the essential 
bleach activator. In particular, novel performance-enhanced bleach 
activators, such as those of Examples III-XII, provide superior results 
and are highly preferred. 
EXAMPLE XXXII 
Bleaching detergent compositions having the form of granular laundry 
detergents are exemplified by the following formulations. 
______________________________________ 
A B C D E 
______________________________________ 
Bleach Activator* 
2.30 3.00 2.30 1.75 2.00 
Sodium Percarbonate 
5.30 0.00 0.00 0.00 0.00 
Sodium Perborate 
0.00 9.00 17.60 9.00 9.00 
Monohydrate 
Linear Alkylbenzene- 
21.00 12.00 0.00 12.00 12.00 
sulfonate 
C4SAE0.68 0.00 0.00 15.00 0.00 0.00 
C2 Dimethylamine 
0.00 0.00 2.00 0.00 0.00 
N-Oxide 
C12 Coco Amidopropyl 
0.00 1.50 0.00 1.50 1.50 
Betaine 
Palm N- Methyl 
0.00 1.70 2.00 1.70 1.70 
Glucamide 
C12 Dimethylhydroxy- 
1.00 1.50 0.00 1.50 1.50 
ethylammonium Chloride 
AE23-6.5T 0.00 2.50 3.50 2.50 2.50 
C25E3S 0.00 4.00 0.00 4.00 4.00 
Conventional Activator 
0.00 0.00 0.00 1.50 0.00 
(NOBS) 
Conventional Activator 
0.00 0.00 0.00 0.00 1.00 
(TAED) 
Sodium Tripoly- 
25.00 15.00 25.00 15.00 15.00 
phosphate 
Zeolite A 0.00 0.00 0.00 0.00 0.00 
Acrylic Acid/Maleic 
0.00 0.00 0.00 0.00 0.00 
Acid Copolymer 
Polyacrylic Acid, 
0.00 3.00 3.00 3.00 3.00 
partially neutralized 
Soil Release Agent 
0.30 0.50 0.00 0.50 0.50 
Carboxymethylcellulose 
0.00 0.40 0.40 0.40 0.40 
Sodium Carbonate 
0.00 2.00 2.00 2.00 2.00 
Sodium Silicate 
6.00 3.00 3.00 3.00 3.00 
Sodium Bicarbonate 
2.00 5.00 5.00 5.00 5.00 
Savinase (4T) 
0.60 1.00 1.00 1.00 1.00 
Termamyl (60T) 
0.40 0.40 0.40 0.40 0.40 
Lipolase (100T) 
0.12 0.12 0.12 0.12 0.12 
Carezyme (5T) 
0.15 0.15 0.15 0.15 0.15 
Diethylenetnaminepenta 
0.40 0.00 1.60 0.00 0.00 
(methylenephosphonic 
Acid) 
Brightener 0.20 0.30 0.20 0.30 0.30 
Sulfonated Zinc 
0.25 0.00 0.00 0.00 0.00 
Phthalocyanine 
Photobleach 
MgSO4 0.64 0.00 2.20 0.00 0.00 
Na2SO4 balance balance balance 
balance 
balance 
______________________________________ 
Any of the above compositions is used to launder fabrics at a concentration 
of 3500 ppm in water, 25.degree. C., and a 15:1 water:cloth ratio. The 
typical pH is about 9.5 but can be can be adjusted by altering the 
proportion of acid to Na- salt form of alkylbenzenesulfonate. Results are 
excellent, particularly with respect to bleaching as compared with 
otherwise identical compositions in which TAED, NOBS or benzoylcaprolactam 
are used at equal weight as a complete replacement for the essential 
bleach activator. In particular, novel performance-enhanced bleach 
activators, such as those of Examples III-XII, provide superior results 
and are highly preferred. 
EXAMPLE XXXIII 
Bleaching detergent compositions having the form of granular laundry 
detergents are exemplified by the following formulations. 
______________________________________ 
A B 
______________________________________ 
Bleach Activator* 2.30 4.60 
Sodium Percarbonate 5.30 12.00 
Sodium Perborate Monohydrate 
0.00 0.00 
Linear Alkylbenzenesulfonate 
12.00 0.00 
C45AE0.6S 0.00 15.00 
C2 Dimethylamine N-Oxide 
0.00 2.00 
C12 Coco Amidopropyl Betaine 
1.50 0.00 
Palm N- Methyl Glucamide 
1.70 2.00 
C12 Dimethylhydroxyethylammonium 
1.50 0.00 
Chloride 
AE23-6.5T 2.50 3.50 
C25E35 4.00 0.00 
Conventional Activator (NOBS) 
0.00 0.00 
Conventional Activator (TAED) 
0.00 0.00 
Sodium Tripolyphosphate 
25.00 0.00 
Zeolite A 0.00 20.00 
Acrylic Acid/Maleic Acid Copolymer 
0.00 0.00 
Polyacrylic Acid, partially neutralized 
3.00 3.00 
Soil Release Agent 0.00 0.40 
Carboxymethylcellulose 0.40 0.40 
Sodium Carbonate 2.00 0.00 
Sodium Silicate 3.00 3.00 
Sodium Bicarbonate 5.00 5.00 
Savinase (4T) 0.00 1.00 
Termamyl (60T) 0.00 0.40 
Lipolase (100T) 0.00 0.12 
Carezyme (5T) 0.00 0.15 
Diethylenetriaminepenta(methylenephos- 
1.60 1.60 
phonic Acid) 
Brightener 0.20 0.05 
Sulfonated Zinc Phthalocyanine 
0.50 0.00 
Photobleach 
MgSO4 2.20 2.20 
Na2SO4 balance balance 
______________________________________ 
Any of the above compositions is used to launder fabrics at a concentration 
of 3500 ppm in water, 25.degree. C., and a 15:1 water:cloth ratio. The 
typical pH is about 9.5 but can be can be adjusted by altering the 
proportion of acid to Na- salt form of alkylbenzenesulfonate. Results are 
excellent, particularly with respect to bleaching as compared with 
otherwise identical compositions in which TAED, NOBS or benzoylcaprolactam 
are used at equal weight as a complete replacement for the essential 
bleach activator. In particular, novel performance-enhanced bleach 
activators, such as those of Examples III-XII, provide superior results 
and are highly preferred. 
EXAMPLE XXXIV 
Bleaching compositions having the form of granular laundry detergents are 
identical to those of any of Examples XXXI-XXXIII. Any of the compositions 
is used to launder fabrics under "high soil" conditions. "High soil" 
conditions are achieved in either of two possible modes. In a first mode, 
consumer bundles of heavily soiled fabrics can be used, the soil level 
being sufficiently high that when a portion of the composition is 
dissolved in the presence of tap-water together with the soiled fabrics in 
a U.S. domestic washing-machine, the pH of the wash water is in the range 
from about pH 6.5 to about 9.5, more typically from about 7 to about 9.5. 
Alternatively, it is convenient for testing purposes when heavily soiled 
fabrics are unavailable, to use the following procedure: the pH of the 
wash bath after dissolution of product and addition of the test fabrics is 
adjusted using aqueous HCl such that the pH is in the range from about pH 
6.5 to about 9.5. The test fabrics are a lightly soiled or clean bundle of 
consumer fabrics; additional test swatches of fabric comprising bleachable 
stains are typically added. 
The fabrics are washed at about 25.degree. C. with excellent results, 
particularly with respect to bleaching as compared with otherwise 
identical compositions in which TAED, NOBS or benzoylcaprolactam are used 
at equal weight as a complete replacement for the *-identified bleach 
activator. In particular, novel performance-enhanced bleach activators 
such as those of Examples III-XIII provide superior results and are highly 
preferred. 
EXAMPLE XXXV 
A bleaching detergent powder comprises the following ingredients: 
______________________________________ 
Component Weight % 
______________________________________ 
Bleach Activator according to any of Examples I-XXX 
5 
Sodium Perborate Tetrahydrate 
10 
C12 linear alkyl benzene sulfonate 
8 
Phosphate (as sodium tripolyphosphate) 
9 
Sodium carbonate 20 
Talc 15 
Brightener, perfume 0.3 
Sodium Chloride 25 
Water and Minors* Balance 
to 100% 
______________________________________ 
EXAMPLE XXXVI 
A laundry bar suitable for hand-washing soiled fabrics is prepared by 
standard extrusion processes and comprises the following: 
______________________________________ 
Component Weight % 
______________________________________ 
Bleach Activator according to any of Examples I-XXX 
4 
Sodium Perborate Tetrahydrate 
12 
C12 linear alkyl benzene sulfonate 
30 
Phosphate (as sodium tripolyphosphate) 
10 
Sodium carbonate 5 
Sodium pyrophosphate 7 
Coconut monoethanolamide 2 
Zeolite A (0.1-1.0 micron) 
5 
Carboxymethylcellulose 0.2 
Polyacrylate (m.w. 1400) 0.2 
Brightener, perfume 0.2 
Protease 0.3 
CaSO.sub.4 1 
MgSO.sub.4 1 
Water 4 
Filler* Balance 
to 100% 
______________________________________ 
*Can be selected from convenient materials such as CaCO.sub.3, talc, clay 
silicates, and the like. Acidic fillers can be used to reduce pH. Fabrics 
are washed with the bar with excellent results.