CA1324558C - Oxidant detergent containing stable bleach activator granules - Google Patents

Abstract

Abstract of the Invention The present invention provides stable bleach activator granules comprising:
a) a peroxygen bleach activator having the structure:

, wherein R is C1-20 branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independently H, C1-4 alkyl, aryl; and L is a leaving group;
b) a pliable binding material selected from materials having a melting completion temperature of greater than about 40°C; and, optionally, c) a filler material.

These bleach activator granules are combined with a detergent base which contains an oxidant bleach to provide an activated oxidant detergent composition.

Description

-` ~324~

Background of the Inventlon 1. Field of the Invention:
This invention rela~es to stable bleach activator granules, specifically, sranules which contain activators with ~he structur*:
O R'O
R-~-O-C-C-L, R~
: 25~ wherein R is C1_20 branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl, substituted aryl, :~ ~ alkenyl~ aryl, alkylaryl; ~' and R~ are independently :H,: Cl_4 alkyl, aryl; and L is a leaving group.
~he~e activator granules are combined with a detergent base ~;: 30 : which comprises builders; and : : a surfactant selected from the group consisting of a~ionic, nonionic, cationic, amphoteric, zwitterionic :~ surfactants, and mixtures thereof: and a b~each-effective amount of a source of hydrogen peroxide to act with the activator granules~ i z. _ ief Descr~e~lR~ot~ 3~
I
Bleach activators have been widely described in the .
~ , .
.

i324~8 literature. For e~ample9 Boldingh et al., U~. 1,147,871, describes bleaching aDd detergent compositions containing an i~organic persalt and acylos~alkyl or acyl benzene sulfonates.
It iS claimed that such esters provide improved bleaching temperatures below 70C ~hen eompar~d to compositions using the parsalt alone.
These activators are r~presented by the formula:

~ 0--C-R

wherein X ~ branched or straight chain alkyl or acyl radical containing 6-17 carbon atoms; R - H or alkyl radical ha~ing 1-7 carbon atoms; and M - an alkali metal, or ammonium radical.

Chung et al., U.S. Pat. No. 4,412,934, discloses bleaching com~ositions containi~y a perosygen bleaching compound and a bleach activator of the ~eneral formula n R-C-L
wherein R iS an alk71 group containing from about 5 to about 18 carbon atoms; I. is a leaving group, 'che conjugate acid of which has a PRa in the range of about 6 to about 13. Chung et ~5 alG focus~s on alk~noylo~y benzene sulfonates, which have been previollsly disclosed in G.B. 864,798, Hampson et al.

Thompson et al, U.S. Pat. No. 4,483,778, discloses bleach activators of the structure Rlo R C-~-L
X
wherein R is C4 1~ al~l, Rl is H or Cl 3 alkyl, X is -Cl, -OCH3, or -OCH2CH3, and L iS a leaving group whose conjugate acid has a PRa of ~-30. The apparently crowded alpha carbon in the T~ompson et al. compound may present hindered perhydrolytic reactivity.

. , , : - . : : - i .

:lL 3 2 ~ 5 ~ ~

~ ardy et al., U.S. 4,681,952, discloses the use o~ a bleach activator compound of the formula [RX]mAL, wherein R is hydrocarbyl, C6 20 alkyl substituted aryl, or alko~ylated hydrocarbyl; X is O, SO2, N(Rl)2, (Rl)P-- O or ~Rl)N--S O, wherein for m=l, A includes O ~ O O ~ O-C-(C~{2)-~ CH=CH-C, or -~- C6H4 -C-, and L can be ol~ybenz ene su 1 f on a t e .

Burns et al., U.S. 4,614,551, discloses the use of a~ide esters of the formula O O O
Rl_C_~-R~ orRl-N-C_R2_C_L, R5 l5 wherein Rl and R2 are alkyl(ene) aryl (ene) or alkylaryl(ene) with 1-14 carbon atoms and ~5 is H, an alkyl, aryl, o-r alkylaryl group with 1-10 carbon ato~.s.

Nakagawa et al., V.S. 3,960,743, disclose polymeric activators having the general structure O B O
R-C-O-(-CH-C-O-)nM, in which R is purported to ~e Cl 16 carbon atoms, a halo- or hydro~yl-substituted Cl 16 alkyl or a substituted aryl group, B
is hydrogen or a Cl 3 alkyl group, M is hydrogen, Cl 4 alkyl or alkali metal, wherein n i5 an integer of at least one when M is an alkyl group or n is an integer of least two when M is hydrogen or alkali metal. The polymeric activators of ~akagawa et al., however, suffer from a fatal defect. ~hey do not disclose, teach or suggest perhydrolysis leavi~nq q~ouPs.
Schirmann et al., U.S. 4,221,675, substituted acylosy N-acetamiBes of the structure ~:

.
- - . . .- .
.. . . : - i . . .

- 132~5~

The activators o~ the present invention do ~o~ contain a nitro~en heteroatom as does the activator of Schirmann et al. Moreover, in Schirmann et all, the group in question, an amide, does not bind to the acyl portio~ of the compound via an o~ygen bond. Schirmann et al3 do not teach or suggest what peracid is generated or where perhydrolysis occurs. Applicants have demo~strated that the alpha acylosy, N-acetylacetamide compounds disclose~ in Schirmann et al.
provide mini~l perhydrolysis at site of the amide ~ond, if at all, and thus do not e~ectively generate the desired peracid, peralka~oylo~yacetic acid. Thus, Schirmann et al. also do not have an eff~tive leaving group.
Yarious refPrences have taught how to ormulate bleach activator granules using activators of ~he p~ior art. For eYample, Corey et al., U.S. 3,661,78g, Gree~ et al,, U.S.
4,009,113, ~e~ers, U.S. 4,087,369, Saran, u.S. 4,372,868, Gray et al., U.S. 4,~99,049, Gr2y, U.S. 4,444,574, Thompson et al., U.S.
4,483,77B, ~hrphy et al., U.S. 4,486,327, Thompson et al., U.S.
4,539,130, Chung et al., E.P. 106,634, Parfomak, U.K. 2,178,075 a~d Divo, l~.S. 4, 681, 695, all discuss ways of combining a perosygen bleach ac~ rator with some binding or enrobing material.
However, none of the foregoing rei~ere~ces teaches, discloses or suggests bleach a~tivator granules with the structure 0 R'0 R~ 0-C-~-L, R"
wherein R is Cl 20 branched or straight chain allcyl, alkoxylated alkyl, c~cloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are indeper~d~ntly H, Cl 4 allc~l, aryl; and L is a leaYing group.

1 3 2 ~

~ oreover, none o the art discloses, teaches or ~uggests that activators of the above structure can be in~orporated in stabilized granules with improved perhydrolysis efficiency over the powdered activator alone. Additionally, none o~ the art discloses, teaches or su~ests that activators o~ this type can b~ ~ranulated with binding materials which have a melting ~ompletion temperature of a~ least about 40C, said binding materials being in relati~ely small quantity with respect to the acti~ator. Also, none of the art discloses, teache~ or suggests that when these activator granules ~re incorporated into a d~tergent base, some deterqent surfactants are preferred over other~, and that certain stabilizing materials are espec;ally preferred.

'~ $umma~Y_Qf the InYentiQn and Q ~ ts ~ he invention provides, in one embodiment, stable bleach activator granules comprising:
a) a pero~ygen bleach activator having the ~tructure:

R-C-o C-C-L~

wh~rein R is Cl 20 branched or ~traight chain alkyl, alko~ylated alkyl, cycloalkyl, alkenyl, 2, aryl, substi~uted aryl, alkylaryl; R' and R~ are independe~tlr ~, Cl 4 alkyl, aryl; and L is a leaving group;
b) a pliable binding material selected ~rom materials having a melting completion temperature of greater than about 40C; a~d, optionally, c) a filler material.

.

, . ~ . ... , ...... - -.

~32~8 . -- 6 --In another embodiment, the invention pro~ides stable bleach activator granules comprisin~:
a) a peroxygen bleach activator ~aving the structure:
5O R'O
Il I ~I
R-C-O-C-C-L, R~
wherein R is Cl_20 branched or straight chain alkyl, alkoxylated alkyl, cycloalk~l, alkenyl, 10aryl~ substi~uted aryl, alkylaryl; R' and R~ are independently H, Cl_4 alkyl, 3ryl: and L is a leaving group;
b) an inorganic or organic binding ~aterial;
whe-e~n said granules are approximately cylindrical or spherical, a~d have a diameter of about 25 ~a 2,noo microns, dissolve, in ~ter, within about lO minutes at 21C, and have a p~ of about 5 ~o 8 in water.
, In still a~other embodiment, the inventi~n provides an ~0 activated oxi~nt detergent comprising:
a) bleach activator granules comprising i) a peroxygen bleach activator haYing the structure:
:~ : O ~'0 : R-~-O-~-C-L, R~ ~.
wherein R is C1~2~ branched or straight chain alkyl9 alkoxy}ated alkyl, cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R~ are independently ~, Cl_4 alky}, aryl; and L is a 30 - leaving group;
ii) a pliable binding material selected from ma~erials having a melting co~?le~ion temperature of greater than about 40C; and, optiionally, iii) a filler material;
: 35 : , . . , . : . :: :

~ ~.32~5~

~ .
b) a ~eterçe~t base ~hich comprises:
i~ bualders;
ii) ~illers;
iii~ a ~urfactant selecte~ from the graup consisti~g o anionic, ~onionic, cationic, amphoteric, æwitterionic surfactants, and mi~tures ther~ ;
and c~ a ~leach-ef ~tive amount of a source of hy~--gen pero~ide, which acts in combination with th~
activator gra~ules of a).

It i~ therefore an object of this invention to proYide stable bleaching actavator granules a hereinbe~ore descri~
lS It is another object o~ this invention to enhance the performance of bleaching ac~i~ator ~ranules as hereinbefore described over that of the po~dered activator.
It is still another object of this i~vention to ~rovid~
bleach activator granules which are easily and efficiently ~o processible.
It is yet another obj2ct of ~his invention to provide ~ ch activator granules which ha~e as a majority of their conte~_, the bleach acti~ator compou~d.
: It:i~ a ~urther object of this invntion to provide an : o~ida~t detergent compGsition which includes the stable bl~
: ~ac~i~ator granules.
: It is a still further o~ject of this invention to impr~-: the laundering performance of said o~idant detergent compo~--ion by careful selectio~ o surfactants.
It~is also an object of this invention to e~ha~ce th~
: perfor~ance of said osidant detergent by careful selection _-~ stabilizing additives.

: rie Des~r~ptiQn Qf the Drawin~s ~: 35 Fig. 1 shows ~ ~low chart d~scribing the manu~acture o~ -he bleach acti~ator granules~

.

132~

~taile~ Pescri~tlon ~ 9fJo~ s~m~e~

The pr~sen~ inven~ion provides stable bleach activator granules compri~ing:
~ a) a peroxy~en bleach activator having the structure:
O R'O
R-C-O-C U L
R
wherein R is Cl 20 branched or straight chain alkyl, alko~ylated alkyl, , cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independently H, Cl 4 alkyl, aryl; and L is a leaving group;
b) a pliable binding material selected from materials having a melting completion temperature of greater than about 40C; and, optionally, c) a filler material.

The parent application, Serial No. 06/928,070, which issued to U.S. Patent 4,778,618, disclosed and claimed the activators which the Applicants process into the present inventive granules. The advantages of said activators are amply discussed in the specification of said application.
While Applicants discuss some of the advantages of said activators in this application, for the sake of brevity, fuller particulars are taught in U.S. Patent 4,778,6180 Additionally o~ interest is the related application of Richard R. Rowland, Serial No. 07/167,544, filed March 14, 1988, entitled "METHOD FOR S~NTHESIZING ACYLOXYCARBOXYLIC
ACIDS," which issued to U.S. Patent 5,091,560 and which discloses methods of acylating the hydroxycarboxylic acids which are predecessors to the activators of this invention.
Of particular interest from U.S. Patent 4,778,618 is a particularly preferred activator, namely, 1~2~

R-~-O-C~2C-~S03M~ ~

These types of activators are referred to as alkanoylglycolate or alkanoyloryacetic acid esters, since their base ~arbonyl group is -OCH2~O.
These types of activators provide numerous benefits ov~r the pr;or art typ~ acti~ators. The ~akagawa et al. type polymeric ac~ivators ~o not teach, dis~lo~e or suggest a leaving ~roup and if their monomer i used as ~a activator, little or no peshydrolysiS occur~. The Schirmann e~ al, ty~e ac~ivators similarly have little or no Ferhydrolysis.
In the following discussion, ~ertain definitions are utilized:
Peracid precursor is equivale~t to bleach activator-. ~oth terms generally relate herei~ to reactive esters whiCh have a lea~ing group substituent, w~iCh during perhydrolysis, actually cleaves of~ the acyl portion of the eeter.
Perhydrolysis is the rea~tion which occurs when a peracid precursor or actiYator is co~bined in a reaction medium (aqueous : medium~ w;th an e~fective a~unt of a source of hydrogen peroxide.
~ 25 ~ The leavin~ group, L, is basically a substi~uent which is : attached via an o~ygen bond ~o the acyl portion of the es~er and which can be replaced by ~ perhydroside anion (OOH ) during perhydrolysis.
The basic reaction is:

R-~-O-C-C-~ ~ OOH -------3 R-~-O-C C-OOH
~n R~

: ', ~324~8 . .

Although further discussion below will elaborate on the unique advantages of the preferred embodiment, 0 R'0 R-C-0-C-C-L, R~
also re~erred to as a glycolate ester or as an acylglycolate ester, at present, the constituent portions of the ester, i~e., the acyl group and ~he leaving groups are herein defined.

R is defined as being Cl_20 linear or branched alkyl, alkoxylated alkyl, cycloalkyl, alkenyl, aryl, substituted aryl or alkylaryl.

It is preferred that R is Cl_20 alkyl or alkoxylated alkyl.
More preferably, R is Cl_10, and mixtures thereof. R can also be mono-unsaturated or polyunsaturated. If alkoxylated, ethoxy (E0) -(-OC~2CH2) and propoxy (P0) -(-OC~2CH2C~

-(-OCH2CH2) groups aré preferred, and can be present, per mole of ester, from 1-30 E0 or P0 groups, and mixtures thereof.

It is especially preferred for R to be from 4 to 17, most preferably 5 to 12, carbons in ~he alkyl chain. Such alkyl groups would be surface ac~ive and would be desirable when the precursor is used to form surface active peracids for oxidizing fat or oil based soils from substrates at relatively low tempera~ures.

It i further highly preferred for R to be aryl and Cl_20 alkylaryl. A different type of bleaching compound results when aromatic groups are introduced onto the ester~

Alkyl groups are generally introduced onto the ester via an acid chloride synthesis discussed in U.S. Pate~ts 4,788,618 and 5,091,560. Fatty acid chlorides such as hexanoyl chloride, heptanoyl ~hloride, octanoyl chloride, nonanoyl chloride, .. :.:., .

~324~5~ ` -.
deca~oyl chlorid~ and the like provid~ this al~yl moiety.
~romatic groups can be i~troduced via aromatic acid chlorides (e.g., benzoyl chloride) or aromatic a~hydrides (e.g., benzoic acid anhy~ride).
S R~ and R~ are independentlY H, Cl_l0 alkyl, aryl~ cl_l0 alkylaryl, and substituted aryl. When R' and ~ are both alkyl, aryl, alkylaryl, substituted alkyl, or mistur~ thereof, pre~erably the total number of carbons of R' ~ R~ dues not esceed about either 20, more preferably does not e~ceed about 1~. Preferably, when R' or R~ a~e carbyl~ne or arylene, the oth~r is H (i.e., unsubstituted). Alkyl of about 1-4 are preferred. If substituted aryl, appropriate substituents include OHJ S03, and C02; NR3+ (Ra is Cl 30 rarbons~ and preferably, two of Ra are shsrt chain (Cl 4) alkyls and one o Ra is a lo~g chain alkyl (C8_3~). Appropriate counterions include ~a~, K+, et~. and appropriate negative counterions include halogen (e.g., Cl ), OH a~d methosulfate. It is pre$erred that at least one of R' and R~ b~
H, and most preferably, both (thus forming methylene).
The parent application stres~ed the impor~ance of the R' and R~ alpha, alpha substituents on the carbylene of the acyl group. This is because the position of various substituents alpha to the pro~cimal carbonyl is very important to the activators .
The leaving group, as discussed above, is basically capable of being di . plaoed by perhydro~side anion in aqueous medium.
Unl;ke prior ar~ precursors, the activator is ~ot limited to leavin~ groups having particular solubility or reactivity criteria due to the reactiveness of the acyl of the inventive precursor. It is, however, preferred that the conjugate acid of the leaving group have a PRa of between about 4 to 20, more pre~erably, about 6 to 15.
Thus, the preferred leavin~ ~roups, none of which are ~eant to lim;t the i~vention, include:
~a) phenol derivatives (b~ halides ~c) osynitrogerl leaving groups (d) carboa:ylic acid ( f rom a mised aI-hydride) ; ` ~3245S~

,.
(a~ Phenol ~rivatives The phenol derivatives can be generically defined as:

~ z wherein Y and Z are, individually H, SO3M, CO2~, SO~M, OH, halo substituent, ORl, R2, NR3X, and mi2tures thereof, wherein M is an alkali meta~ or alkaline earth counterio~, Rl of the ORl substituent i~ Cl 20 alkyl, R2 is Cl 6 alkyl, R3 of the NR3 substituent is Cl 30 alkyl, X is a counterion there~or, and Y and Z can be the same or different.

The alkali metal counterions to sulfonat~, sulfate or li carbonate (all of which ar~ solubilizing groups~ include K+, Li~ and most preferably, Na+. The alkaline earth counterions include Sr++, Ca~+, and most preferably, Mg+~. Ammonium (NH~) and other positively charged counterions may also be suitable. The halo substituent can be 2~ F, Br or most preferably, Cl. When OR~, alkosy, is the substituent on the phenyl ring, Rl is Cl 20~ and the 2 criteria defined ~or R on the acyl group apply. When R is the substituent on the phenyl rin~, it is a Cl 1~ alkyls with preference ~iven to methyl~ ethyl, n- and iso-propyl, n-, sec-and tert-butyl, which is especially preferred. When -~3X, quaternary am~onium, is the substi~uent~ i~ is preferred that two of R3 be short chain alkyls (Cl 4, most preferably, methyl) an~ one of the R3 alkyls be longer chain alkyl (e.g., C8 30)~ with X, a negative counterion, preferably selected from halogen (Cl-, F~, Br~, ~~), CH3SO4 (msthosulfate~, NO3, or OH .
Especially preferred are phenol sulfonate leaving groups. A
preferred synthesis of phenol sulfonate esters which co~ld be adapted ~or,use herein i5 disclosed in Zielske, U. ~. 4,735,740 commonly assigned to The Cloro~ ~ompany.

.. ........ . . ....

r ~on-limiting preferred phenol derivatives are:

~O { O } SO3M (sodium p-phenyl sulfonat~) -O ~ OH (p-, o- or m-dihydroxyb~nzene) -O ~ C~CH3)3 (t-butyl phenol) ~b) ~alid~
The halide leaving groups arP quite reactive and ac~ually are directly obtained as the intermediates in the synthesis of the phenyl sulfonate and t-butylphenol esters. While halides include Br and F, Cl is most pre~erred. A non-limiting e~ample i~:
- -Cl (chloride) (c) O~Yni~roqen The osyn;trogen leaving groups are preferred. In the co-pending application en~itled UAcylosynitrogen Peracid ~:` Precursors,~ inventor Alfred G. Zielske, commo~ly assigned to : The Cloros Company, Oa~land, California, filed concurrently herewith, Ser. No. 06/928,065, which issued to U.S. Patent 2.~ 4,957,647, a detailed description of the synthesis of these leaving groups is disclosed. These oxynitrogen leaving groups are generally disclosed as -oNR5, wherein R5 comprises at least one carbon which is singly or doubly bonded directly to N.
:~ 30 ~ 35 . ~

324~S8 -oNR5 is more specifically defined a:
;R6 -ON=C
`~R7 Q~

~ o r -ON R l O
ll-R9 ~ C
O O

~Ydro~.imide -ON--R14 or -ON R16 R15 3 ~C
Amin~ Q;~i~
~ leaYing groups ~lave the structure : R 6 : :
-ON=C
: ~R7 wherein R6 and R7 are individually H, Cl 20 alkyl, ~which can be cycloalkyl, straight or branched chain), aryl, or alkylaryl and at l~ast one of R6 and R7 is not H.
;~ 30 Preferably R6 and 127 are the same or different, and ran~e rom Cl 6~ O~imes are generally derived ~rom the reaction of :: ~ hydro:~ylamine with either aldehydes or ketones.
: '~

~ 35 ~

- ,. , . ~ , ,,, , .. , ~ , - . . . .. . ,, ." . . :

- ~3245~8 ~ on-limiting esamples of an ox~me leaving group are: Sa~
o~im~s of aldehydes (aldo~imes), ~.g., acetaldo~ime~
be~zaldosime, propionaldo~ime, but~laldo~ime, heptaldo~ime, he~aldo~ime, phenylacetaldosime, p-tolualdoxime, anisaldo~ime, S caproaldo~ime, valeraldo~ime and p-nitrobenzaldoxime; and (b) os~mes of ketones (ketosimes), e.g., acetone osime (2-propanone osi~e), meth~l ethyl keto~ime (2-butanone o~i~e), 2-pentanone osLm2, 2-he~anone oxime, 3 hesano~ osime, cyclohe~anone osime, ace cphenone o~ime, benzophenone o~ime, and cyclopentanone ~ o~ciIoe .
Particularly preferred o~ime leaving groups are:

,_____ CH3 ~ CH3 -o~ o~-c\
CH3 ~2CH3 Ace~ne ~xime ~Qthylethyl K~o~ims ~L~Yim~ leavin~ groups co~prise:

~ R8 or _~ / R10 \~~-R9 `
Q
~ herein ~8 and R9 can be the same or different, and are preferably straight chain or branched Cl ~ alkyl, aryl, alkylaryl or ~i~tures thereof. I~ alkyl, R and R can be partially unsaturated. It is especially preferred that R8 and R9 are xtraiqht or branched chain Cl 6 alkyls, which can be the same or different. R10 is preferably Cl 20 alkyl, aryl . . ~ , , :.- , ,,: . .

~324~
.- 16 or alkylaryl, and completes a heterocycle. ~lO includes the preferred structure O

-O-N
o wherein Rll can be an aromatic rlng fused to the heterocycle, or Cl_6 al~yl (which itself could be substituted with water solubilizing groups, such as EO, PO, CO2 and SO3~.

Thess esters of imides can be prepared as ~escribed in Greene, Protectiv~ ~r~Ps in ~rqani~ Svn~hesis, p. 183, and are generally the reaction products of acid chlorides and hydroxyimides.
No~-limiting e~amples of N-hydro~yimide which will provide the hydro~yimide leaving groups of the invention include:
N-hydro~ysuccinimide, N-hydro~yphthalimide, N-hydroxyglutarimide, N-hydro~ynaphthalimide, N-hydro~ymaleimide, N-hydroxydiacetylimide and N-hydrosydipropionylimide.

~specially preferred examples of hydro~yimide leaving groups are:
O O

-O-N ~ -O-N

O
Q~y ~ç ~ . Oxyphthalimide Q~igg leaving groups comprise:
: ~ R ~ C
35-ON -R14 or -ON - Rl~ R15 :~ \ R13 ~J

:

.

` 132~8 I~ the first preferred structure far amine o~ides, R12 and R13 can be the same or dif~erent, ana are pre~erably Cl 20 straight or branched chain alkyl, aryl~ alkylaryl or mi~tures there~f. I alkyl, the substituent c~uld be partially S unsat~rat~d.
Preferably, Rl~ and R13 ar~ Cl 4 alk71s and can be the same ~r different. R14 is preerabl~ C~ 30 alkyl, aryl, alkylar~l and mistures thereof. This ~ substituent could also be partially urlsaturated. It is D~ost preferred that R12 and R13 are relatively short chain alkyl ~roups (CH3 or CH2CH3~ aIld ~14 is preferably Cl_20 alkyl, forming togeth~r a tertiary amine oside.
F~r~her, in the ~econd preferred amine oside structure, R15 c23 be Cl 2~ alkyl, aryl or alkylaryl, and completes a heter~c~cle. R 5 preferably completes an aromatic heterocycle of 5 c~rbon atoms and can be Cl 6 alk~l or aryl substituted.
R 6 is ~referably noth;ng, Cl 30 alkyl, aryl, alkylaryl or mi~tures thereof. R is ~ore preferably Cl ~g alkyl if ~5 ccm~letes an aliphatic heterocycle. If R completes an aromatie h~terQcycl~, R16 is nothing.
Nc~-limiting esamples of amine o~idQs suitable for use as leavi~ groups herei~ can ~e derived from: pyridine N-o~ide, ~ trimethylamine ~-o~ide, 4-phenyl pyri~i~e ~-o~id~, decyldimethyl-amine ~-oside, dodec~ldimethylamine ~-oside, tetradecyldimethyl-amine ~-o~ide, hesadecyldimethylamine D-o~ide, octyl~i~ethylamine N-o~ide, di~decyl)~e~hylamine N-o~ide, di(do~cyl)methylamine ~-oxide, di(tetradecyl)methylamine N-osi~e, 4-picoline N-oside, 3-picoli~e N-oside and 2-picoline N-osiae.
3~ Es~ecially preferred amine oside leaving groups includ~:

-O-N ~ _O ~ ~

P~-idinium ~-Q~ide Phen~1~2ridinium ~-oside ... ., ~ :

132~5~8 ~ 18 -~d) ~arbQ~yli~ A~ fr~ M;~ Anh~drides Carbosylic acid leaving groups have the structure O
-o-lc-Rl7, wherein R17 is C~ alkyl, preferably Cl 4 alkyl, most pref~rably either CH3 or CH2CH3 and miitures thereof .
When R17 is Cl and above, it is be~ iesred that the leaving groups will form carbosylic acids upon perhydrolytic eonditions. Thus, when R17 is CH3, acetic acid would be the leaving group; when CH2C~3, propionic acid would be the lea~ing qroup, and so on. However, the foregoing theory is non-binding and offer~ o~ly one e~planation for what may be a very complicated reaction.
Non-limiting e~amples of mised anh~dride esters include:

R-C-O-CH2/;~
CH3l~
O
~lk~noylo~y a~ic~cetic acid mi~ed_~nhydride;

~0 s 132~

o o O-C H

CEI3CH2 ~/

Alkanoylo~Ya~e~ic/P~QPionic ~id ~e~ anhYd~i~e.

~v~n~g~s of_~hçLE~3~ ch Activa~or As previously described in the parent application, U.S.
Ser. No. 06~928,070 which issued to U.S. Patent 4,778,618, the activator provides numerous advantages over tbe prior art. For one, the activator is not tied to critical ratios of hydrogen peroxide source to activator, as are the fatty acid esters of Chung et al., U. S. 4,412,93~.
Additionally, because the activ2tor presents multiple acyl ~unctionalities, it can provide môr~ than one type of peracid, thus boostin~ performance in launderins applications. For instance, a preferred activator, octanoylo~yaeetat~, phenol sul~onate ester, can give rise to three diffsrent peracids:

CH3(CH2)6~-0CH2c ~ -S03~a ~ OOH

~ CH3(CH2~ O~B2C-OOH ~ o ~ S03Na I. peroctanQYlo Yac~tac a~id -~o~

~3~CH2)6~ 00 HOCH ~ OOH
II. ~ctanoi~ a~id III. ~ qyloli-~id ~: The prior art materials cannot provide thes~ advantagesO
~ ' ;: 35 . ~ , . .. - . ~ :
~ ~;,: ., .

. ~,... . .

~:

~32455~`
.
. - 2 For instance, one fa d ally similar, but entirely inferior acti~ator is disclosed i~ Schirmann et al., U. S. 4,221,675. A
product coming within Schirmann et als disclosure was synthesized, alpha-octa~o~l, N-acetylacetamide, and perhydrolysis S studies were conducted to see what reactions were being generated. In conducting the study, it was assumed that perhydrolytic attack on the compound cou~d take place at one sr all or a ~ombination of three sites:
O O H O
CH3(CH2~fi~-O~H2C-~-C CH3 (CH2~6~-OOHCu3~cH2)6U-OcH2c-OOH 1' eroctanoic acid perQ~tanovlo~vacetic acid perace~i~ acia'5 SITE ASITE B SITE C
Three moles of hydroge~ peroside per mole of activator ~one per car~onyl site) were reacted with this alpha-octanoylosy, ~-acetylacetamide.
Tallying the reactio~ products via high performance liquid 2~ .
~ chromatography ~HP~C) us1ng an adaptation of the potentiometric methods set forth in Isaa~son et al, "Reaction Detector for Liquid Chromatography wi~ lectrochemical Generation a~d Detection of ~scess of Bromin~, R ~ chromat,oqFaPhY~ Vo ~ 324, pp.
333 et seq. (1986), the results were:
~5 .,~ ~ . , .. , ~ .

- ~32~5~8 TABLE I
Perhydrolysis Profilel of . ~ tanoy~-acetYl~e~3~is~

15~=oL~L~ fi~ .5 2~ 5 Peroctanoic ~cid A 27.3% 8.60~0.83.
~eroctanoyl~yacetic Acid B 2.1% 0.59% O.oO~.
Peracetic Asid C 9.1% 5.3% 0.20.
Octanoylo~cetic Acid hydro- 55.0% n/a2 n/a2 lysis ~t ~

1 Assuming ~ree perhydrolytic sitas, 14 p~m A.O. theor~tical ma~imum ~ield. HPLC at 13 minutes.
2 not avail~hle Review of the above discloses that the m~jor reaction of the compound alpha-octanoylo~y, ~-acetylacetamide is hYdrol~is, not perhydrolysisc Additio~ally, primary sites for perh~drolysis are at a and c, ~eaning that site b.is very i~efficien~. This is to be compare~ ~ith one of the preferred acti~ators, octanoyloxy acetic aci~; phenyl ~ulfonate ester, whi~h has the majority of p~rhydrolysis a~ ~ite B, little a~ ~ite A:

' i324S~8 `

CH3~CH2)6c-ocH2c ~ O } ~O3~a A B
Table II
Perhy~rolysis Prof i le ofl PH _ P~ra~id/P3rOd~lG~ 1~2 lg, 53 ~, 54 ~5 Peroctanoic Acid 4% 10% 4~ 3%
Peroctanoylo~yacetic Acid59% 55% 62~ 41%
P~rglycolic Acid 5% 11% 3~ 3~
Octanoylosyacetic Acid 23% 15% 15%~ 32%

1- 1 Date obtained fr~m HPLC; 2:1 pero~id_ : precursor ratio, ~2sed on two minu~es from start from p~rhydrolysis.
2 Initial precursor concentration: o . RmM
: 3 Initial precursor concentrat;on: 6.0m~

4 Initial precursor concentration: 6.0mM
:: 5 Initial precursor concentration: 6.0mM
6 Estimated-2~ ~a~agawa et al.,:U. S. 3,960,743, discloses contended Dl~ach ~ acti~ator~i of the structure:

!:~ o B O
R~ CH-C-O-)nl~, ~ 30 in which B is H or Cl 3 alkyl, ~ is Cl 4 alkyl, ~, or alkali ,: me~al sialt. This structure ~an ~e divided into two cate~o~i~s:
T ~1) when M is~Cl 4 alkyl, ~ can be 1, thus providing a~ al~yl ,~ ester of acylglycolic acid; and ~2~ when M is H or alkali ~al salt, n must be great~r tha~ lo thu~i the compound must be I 35 polymeric~

,i :
, , ,, .. . . -:. ~ .. .. , . . , , . . - ~, ` 132~5~

In the case o~ (1), ~ completing ~n alkyl e~ter, it is clear that M does not function as a lea~in~ ~roup. Alkyl al~ohols are not leavinq groups.
In the case of ~23, M is H or alkali metal salt, these again S do DQ~ functi~n as leaving groups.
In the cas~ where M is H or alkali metal salt, a compound which is repr~sent~ive of Nakagawa et al, nam~ly, octanoylo~yac~tic acid, was tested for perhy~rolytic performance.
(I~ placed in an alkali~e medium, this acid ~ould be neutralized, i.~., deprotonated, and would form the alkali ~etal salt. Thus, this compound is repres~ntative of either M is H or alkali metal salt.~ Octa~lo~yacetic acid has the structure O
CH3~CH2)6C-OCH2l-OH.
The c~E~ound can be synthesized as described in the parent application, S~rial No. 06/928,070, at pages 33-34 thereof.
In test;~g this representative compound, the following conditions ~ere used:

Octano~ yacetic Acid: B.75 X 10-4M (dissolved in 3 ml o~ 50~50 vol.~vol.
diosane/wat~r) Hydroge~ Pero~ide: 1.65 X 10-3M
Temperat~re: 21C
pH: 10.5 ~5 Buffer: ~.02 M (NaCO3~aHCO3~
Thus, 1.9 ~oles o~ H202 per mole of this ~activatorn were placed in aque~us solution.

3~ Tallying t~e reaction produ~ts via high per~ormance liquid chromatograph~ (HPLC3 using an adaptation o~ the potentiometric methods set forth in Isaakson et al, ~Reactio& Detector for Liquid Chromatography with ~lectrochemical Ge~eration and Detection of ~2cess of Bromine,~ C~hro~a~?~aPhY, Vol. 324, pp.
333 et seq. ~19863, the results were:

~ - . . .

~3245~8 TABLE III
PerhydrolYsis Profile of OctanoYlox~acetic A~id .

TimeTotal A.O.l Peracid2OctanoySosyacetic Acld3 (min,~ConcentrationConcçntr~tion~oncentration 1.76mM N/D4 0.85mM
1.52mM N/D4 0.~4mM
1.64m~S N/D4 0.88mM

1 Total Activs O~ygen (nAO~) concentration (mM) determined by iodide~thiosulfate titration using molybdate catalyst; includes H22 and peracids.
2 Peracid concentration (mM~ determined by iodide/thiosulfate titration after treatmert with catalase enzyme lS to eliminate the hydrogen pero2ide.
3 Concentration (mM) measured by ~PLC.
4 Not detected; additionally, no peracids were detected by HPLC (detection limit is 0.001 mM).
?
Thus, as seen from the above, neither Schirmann et al. nor Nakagawa et al. provide the benefits o~ the activators of the invention.

.

'~;

:, . , , . . . - ..
.: , . . .

: : . ~ i . ; ;
., : ~ - : :

- -~3-24~

~ Ble~ch A~iYa~o.r ~les While it has been disclosed by Applicants in the parent appl;cation, that substitllting solubilizing groups may improve th solubility an~ enhance the reactivity of the activators, the present ;n~entio~ concerns combining the activator with a sui~abl binding material in order to form granules which are stable upon storage and whi~h form peracid more efficientl~.
The granul*s are formed by ~ombining the hereinbefore-described actiYators with pliabl~ binding materials having a melting ~ompletion temperature of at least about 40C. It is pref~rxed to i~clude a filler material which can control solubility o ths granule and for good handling characteristics.
13 1. ~ 3LI~L-CLi l The b~nder material is critical to the invention. It should be an organic ma~erial which has a melting completion temperature ~melting point) above about 40C, more preferably above about 50C. The material should not react with either the ~ activator, or, if the granules are ~ombinéd with an osidant-containiAg detergent, with the compone~ts of such detergent duri~g storage thereof. The binder should idaally have low hygrosco~i~ity, yet b~ $oluble or dispersible ln aqueous . solution, preferably at low temperatures. The binder should also be able to ~or~ a paste or doughy mass suitable for forming noodles, and after processing, granul~s. Workability, viscosity, pliability, and mis~ibility in water, of the bi~der should be optimal, depending on th~ process used.
Types of materials suitable for use include, without limitation:

~32~5~

Q~g~ni~ MatQ~L~

1. Nonionic Surfactants.
2. Anionic Surfactants~ -3. Cationic Surfactants.
4. Film-forming polymers.

5. C12-C18 Fatty acids or salts thereof.

6. C12-C2~ Aliphatic alchols.

7. Relatively low molecular weight polyethylene glycols (2 t 000-10 ~ 000) .
B. Sodium alkyl glyceryl ether sulfonate (sodium coconut oil, fatty acids monog~yceric sulfonates and sulfates); sodium alkyl ether sulfa~ates; alkylphenol-ethylene o~ide ether sulfate; and esters of alpha-sulfonated fatty acid.
9. Acrylic acid, hydro~yacrylic acid, methacrylic acid polymers; co-polymers of ethylene styrene and vinyl methyl ether ~e.gs., Versicol & Gantrez).
10. Cellulose acetate esters, cellulose acetate sulfate, cellulose sulfates, hydroxyethyl cellulose sulate, methylcellulose sulfate, hydro~ypropylcellulose sulfate.
11. Starch, starch/ether.
lZ. Sodium carbosymethyl cellulose.
13. Polyvinyl alc~hol.
14. Gelatin.
15. HP~ (National Starch ~ Chemical Corp., (an 3~ amylopectin food starch).
16. Cross-linked pre-~elatinized amylope (e.g., Clearjel, National Starch ~ Chemical Corp.).

., ~

~32~5~

The binder material imparts physical integrity to the particle which is important in particle crush durability. Although organic ~, binders are preferred, certain silicates may also bZe suitable for use. Other binders disclosed in Chung et al., European Patent S 106 634, publishe~ April 25, 1984, are suitable for use. The , bZinder also aids in the dispersion of the particle and .l solubilization o~ the precursor. Preferred binder materials were s selected from the following classes of compounds: Calsoft*F90, ~ Calsof~ L40 and Biosoft*D62 rom the linear alkylbenzene .~ 10 sulfonates; Carbowa~*3350, 4600 and 8000, ~rom polyethylene glycols; Span 40*from substitute~ sorbitans; Triton*CF54 from alkyl aryl polyetho~y adducts; Pluronic*F125 from block copolymZers of propylene and ethylene oxide; Alfonic*1618-80, Brij*-58, and Neodol*45-13 Erom etho~ylated ~lcohols; sodium palmitate from ;,, 15 fatty acid salts; and polyacrylic acid. Of these the Calsoft i' materials, Alfonic*1618-80 and Carbowa~*4600 (polyethylene glycol, Mol. wt. ~ ~,600) were found to b~ most preferred. The especially preferred binding materials consist of a 50/50 wt./wt. combination of Calsoft*L40 (a Cll 5 linear alkyl benzene ~ulfonate, sodium ,`~,J~ 20 salt, 40% active, from Pilot Chemical Co.) and Alfonic*1618-80 (a sZ el6 18 ethoxylated alcohol, with about 10.7 moles of ethylene !~ o~ide per mole of alcohol, 100% active, rom vista Chemicals); and Carbowa~*4600 and Calsoft*L40 in 50~50 wt./wt. mi~ture, based on ~; actives.
2. Fill~r/~iluent-A fill~r or diluent can be used to control solubility of the granule and to assure optimal processibility of the noodle.
The diluent also helps in the dispersion of the precursor by '30 allowing the particles to break up more readily when placed into an aqueous medium. The nature of the diluent should b~ such that it does not react ~ith the other components o~ th~ particles, is ~ readily solu~le, not hy~roscopic and can he powdered to the same î mesh size as the precursor. The filler is any inert salt such as ~3s Na~SO~, Na2CO3, ~aCl, boric acid, bora~, and oth~Zr alkali .,.
~.j *Trade Mark .,, r~
, .
, , . . :
, ... ~ . , : , -132~5~

metal salts. It is preferable that water~insoluble materials be limited, e.g,, CaC03, MqCO3, etc.
3. Formin~ the ~ranules ~he activator, binder and diluent/filler are combined, usually with additional water talthough some bi~ders, e.g., surfactants, are supplied by manufacturers as aqueous solutions, so the amount of added water can be limited or varied as needed) in order to for~ a workable paste or doughy mass.
The process of preference is referred to as e~trusion, in which material as hereinbefore described are processed into a doughy mass and e~truded through a dieplate or other sizing means to form long noodles. Such noodles are then dried and chopped or vibrated or otherwise formed into granules. Alternatively, the qranules could be formed by agglomeration or spray be~ process, both of which form a part of the invention.
The noodles are prepared by first dry mising the solid components o~ the formulation, which includes activator, diluent, and optional colorant, to form an evenly distribute~ dry powder.
This mi~ture is ~hen added to a fluid hot melted ~inder or to a warm aqueous solution of binder to form a doughy mass. The douqhy mass can be further moistened to aid processinq by the addition o~
2-15~ water by weight o the misture. The substantially homogeneous mass is ~hen estruded through a .25mm-2mm diameter die hole. Noodle e~trudate is then dried to a water content of preferably less than 3~ by weight of the processed noodle. The dried noodles are then chopped down to lengths not greater than 5 mm .
By reference to Figure 1, a flow diagram of the process, a simplified description of a non-limiting embodiment of the process can be demonstrated. The dry components (activator, diluent and optional colorant) are ~ry-mi~ed to form a dry pr2ble~d 2.
Secondly, the liquid componen~s (surfactants, polymers, i.e., binders, and water) are mi~ed to form a liquid preblend 4. These two product streams arP added in a mi~er 6 which forms the doughy mass. The mass is passed through to an e~truder 8. This can - ~ ... .

:

, ~ :,~ , :

` ~32~558 ~9 comprise an inverted-funnel-shaped hopper provided ~ith ~cre~ in the bottom thereof. The screw~ work the mass and channel ;t to a die plate, grate, or other means of rcducing the mass size. A~
the mass iS forced out of the dîe, it produces lon~ Rnoodles,~
S which then fall into a sizer 10. The sizer can ~e a shaker b~d, which is a vibratinq ~ed which breaks the noodles up into the desired shapes and si~es o~ granules. The sizer could alternat;vely be a continuous conveyor or combined With a ~ibrator or with a spike to break up the noodles, in which case the process can be conti~uous ~the conveyor could carry off the desire~
particles, while the fines could be recycled.) The fines, particles less than about o.l mm in length, could be shaken o,f to a collector 12, which preferabl~ recycles the fines to the e~truder 8. The.granules ~ou1d then be dried in a drier 1~, then 1~ outputted to a collector 18, ~ith fines again sipho~ed off ~ia a fines collector 14, which preferably ecycles such fines. Th-~inished granules 20 are then packaged or further taken via conveyor to be combined with the detergent base.

4. The Gr~nul~s The granules have increased storage stability over unprocessed precuirsor, good crush durability properties and dissolve readily in ~he wash water. The noodle particles pre~erably comprise rom 50-99, more pre~era~ly 80-97 percent precursor, from 0.5-25 more preferably 3-15, percent binder, fr~m 0-25, more preferably 0-5, most pre~erably .1 5, percent dilu~n~
and from 0-5 percent ~atPr based on the weight of the process-d noodle. An optional colorant can also be present in the n~odle in the range of from 0-5 percent by weight of the processed noodle.
~11 ingredients of this particle composition are evenly distributed throughout the par~icle.
The granule size is an important factor in storage stabil~ty and solubility of the ~article. It is preferred ~hat the ~oodles ha~e a diameter in the range o 2 to .25, more prefera~ly 1.5 to , , ., :, ,: ` :,', : . ' ':: . . : :',. ' ,:

:: : . ' : ` ' ' . : . '': :''~,: ` , ::,:, ::

132~8 0.3, most preferably 1.0 to 0.5 mm. Optimally, they will be 0.75 mm in diameter. The length of the particle is preferred to be from 0.1 to 5 mm, more preferably 0.5 to 3 mm long. The particles are preferably cylindrical in shape. Alternatively, they may be spherical, with the preferred diameters giYen above.
In the granules, the proportions of ingredients should be preferably between 99:0.5:0.5 to 50:25:25 activator: binder:
diluent, more preferably 98~ 75:12.5:12.5. High amounts of activator are desirable in order to enhance the finished p~oduct's performance and to reduce the overall percentage of activator granules in the detergent for cost efficiency. The particles should dissolve in water within about 10 minutes at 21C.

5. The Deterqent_ÇomPosi~ion~
l; The activator granules o~ the invention are combined wi.h a detergent base, said base comprising:
builders; and a surfactant selected from the group consisting of anioni~, nonionic, cationic, amphoteric, zwitterionic surfactants, and mi~tures thereof; and a bleach-effective amount of a source of hydrogen pero~ide to interact with the activator granules.
Each of these components, and adjunct materials suitable for use herein are ~urther discussed below:
6. Builders The builders are typically alkaline builders, i.e., those which in aqueous solution will attain a pH of 7-14, preferably 9-12. Esamples of inorganic builders include the alkali metal and ammonium carbonates (including sesquicarbonates and bicarbonates), phosphates (including orthophosphates, tripolyphosphates and tetrapyrophosphates), aluminosili~ates ~both natural and synthetic zeolites), and mi~tures thereof. Carbonates are especially desirable for use in this invention ~ecause of their high alkalinity and effectîveness in removing hardness ions which may be present in hard ~later, as well as their low cost. Carbonates .....

~3~5~

i can be used as the predominant builder. Silicates.(Na2O:SiO2, modulus of 4:1 to 1:1, most preferably about 3:1 to 1:13 can also be used. Silicates, because of their solubity in water and ability to form a glassy matri~, can al50 advantageously used as a binder for the detergent.
Organic builders are also suitable for use, and are selected from the group consisting of the alkali metal and ammonium sulfosuccinates, polyacr~lates, polymaleates, copolymers of acrylic acid and maleic acid or maleic anhydride, citrates and 10 mi~tures ~hereo.

7, Fillers/Diluen~s ~he same materials as used in the manufacture of the granules can be used herein as fillers for the detergent. Salts 15 such as NaCl, Na2SO4, and boro~, are preferred. Organic diluents, such as sugar, are possible.

8. ~rfa~tants Particularly effective surfactants appear to be anionic 20 surfactants. Esamples o~ such anionic surfactants may include the ammonium, substituted ammonium te.g., mono-, di-, and tri-ethanolammonium), alkali metal and alkaline earth metal salts of C6-C20 fatty acids and rosin acids, linear and branched alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates, 25 alkane sulfona~es, olefin sulfonates, hydro~yalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates and acyl N-methyltaurides. Preferred are aromatic sulfonated surfactants. Of particular preference are linear and branched C6 18 alkyl benzene sulfonates, both the 30 salts thereof as well as the acidic form. Most preferred are the acidic al~l benzene sulfonates such as Biosof~ Sl00 and S130, with the latter especially preferred.
Other preferred surfactants of use include linear ethoxylated alcohols, s~ch as those sold by Shell Chemical Company under the brand name Neodol* Other suitable no~ionic surfactants can inelude other linear etho~ylated alcohols with an average length *Trade Mark , .

-- 132~

of 6 to 16 carbon atoms and averaginq about 2 to 2n moles of ethylene o~ide per mole o alcohol; linear and branched, primary and secondary ethoxylated, proposylatsd alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oside and about 1 to 10 moles of propylene o~ide per mole of alcohol; linear and branched alkylphenosy (polyetho~y) alcohols, otherwise known as etho~ylated alkylphenols, with an average chain length o~ 8 to 16 carbon atoms and averaging 1.5 ko 30 moles of ethylene oside per mole of alcohol; and mi~tures thereof.
Further suitable nonionic surfactants may include polyoxy-ethylene carbo~ylic acid esters, fatty acid glycerol esters, fat~y acid and etho~ylated fatty acid alkanolamides, certain block copolymers of propylene o~ide and ethylene oYide, and block polymers of prop~lene o~ide and ethylene o~ide with proposylated ethylene diamine. Also included are such semi-polar nonionic surfactants like amine o~ides, phosphine o~ides, sul oxides, and their etho~ylated derivatives.
Suitable cationic surfactants may include the quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C12-C18 alkyl group and the other three groups are short chained alkyl groups which may bear substituents such as phenyl groups~
Further, suitable amphoteric and zwitterionic surfactants which contain an anionic water-solubilizing group, a cationie group and a hy~rophobic organic ~roup may include amino carbo~ylic acids and their salts, amino dicarbosylic acids and their salts, alkylbetaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds. Other e~amples of potentially suitable zwitterionic surfactants can be found described in Jones, U.SO
4,005,029, at columns 11-15.

, .:, ... . .. . . . . . ..
:: , . . ~ , . - : , . :
~i; . .. : ~

- 13245~

Further e~amples of anionic, nonionic, catio~ic and amphoteric sur~actants which may b~ suitable for use in this invention are depicted in Xirk-Othmer, EncyclQpedia o~_Chemical TechnQlogy, Third Edition, Volume 22, pages 347-387, and c~u~h~Qn~
Det~rqents and Emulsifiers, North American Edition, 1983.

As mentioned hereinabove, other common detergent adjuncts may be added if a bleach or detergent bleach product is desired. If, for example, a detergent composition is desired, the following ranges (weight %) appear practica~le:

0.5-50.0% Hydrogen Pero2ide Source 0.0S-25.0~ Precursor 1.0-50.0% Surfactant 1.0-50.0~ Build2r 5.0-99.9% Filler, sta~iliæer~, dyes, Fragrances, brighteners, etc.

9. Hvdroqen_Pero~ide So~rce The hydrogen peroside source may be selected from the alkali metal ~alts of perearbonate, perborate, persilicate and hydroge~
peroside adducts.
Most preferred are sodium percarbonate, and sodium perborate mono- and tetrahydrate. Other perosygen sources may be possible, such as alkaline ~arth a~d alkali metal pero~ides, monspersulfates and monoperphosphatesO
The ranqe o~.pero~ide to activators is preferably determined as a mo~ar ratio of pero~ide to activator. Thus, the range of pero~ide to each activator is a molar ratio of from about 1:1 to 20:1, more preferably about 1:1 to 10:1 and most preferably about 1:1 to 5:1. This is also the definition of a bleach effective amount of the hydrogen pero~ide source. It is preferred that this activator pero~ide composition provide about 0.5 to 100 ppm peracid A.O., and most preferably about 1 to 50 ppm peracid A~O., and most preferably about 1 to 20 ppm peracid A.O., in aqu~ous media.
A description of, and explanation of, A.O. measurement is 3s found in the arti~le of ~heldon ~. Lewis, ~Peraci~ and Peroxide O~idations,~ In: O~idation, 1969, pp~ 213-2S8, i .
.

, : -, , . . . , . ., - . .. . ~ . . .
. .
: . , , , ~ .. ~ . .

~32~

Determination of the peracid can be ascertained by the analytical techniques taught in Organic Peracids, (Ed. by D.
Swern), vol. 1, pp. 501 et seq. (Ch.7) (1970).
101 Chelatinq ~q~n~
In some of the compositions herein, it is especially preferred to include a chelating agent, most prefera~ly, an aminopolyphosphonate. These chelating agents assist in maintaining the solution stability of the activators in order to achieve optimum perhydrolysis. In this manner, they are acting to chelate heavy metal i~ns, which cause catalyzed decomposition of the in situ formed peracid, although this is a non-binding theory of thsir action and not limiting to Applicants. The chelating agent is selected from a number of known 39ents which are effective at chelating heavy metal ions. The chelating agent should be resistant to hyd olysis and rapid o~idation by ogidants. Preferably, it should have an acid dissociation constant (pKa) of about 1-9, indicating that it dissociates at low pH's to enhanc~ binding to metal cations. The most preferred chelating agent is an am;nopolyphosphonate which is commercially available under the trademark Dequest, from Monsanto Company.
E~:amples thereof are Dequest 2000, 2041 and 2060. (See also Bossu, U.S. 4,473~S070 column 12, line 63 through ~olumn 13, line 22. A plyphosphonate, such as Dequest 2010, is also suitable for use. Other chelating agents, such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) may also be suitable for use.
Mistures of the foregoin~ may be suitable. Effective amounts of the chelating a~ent range from 1-1,000, more preferably 5-500, most preferably 10-100 ppm chelating agent, in the wash liguor.

11. Adiun~ts:
The standard d~tergent adjuncts can be included i~ the present invention.
~hese include enzymes are especially desirable adjunct materials in ~hese detergent products. However, it may be preferred to include an enzyme stabilizer~

;- . , - ~ , ~. : : . , : : , ; : ~ : ..

` _-35 _ ~32~5~

Proteases are one especially preferred class of enz~mes. They are select~d ~rom acidic, neutral and alkaline proteases. The terms ~acidic,~ ~neutral,~ a~d ~alkaline,~ refer to the pH at which the enzymes' activity are optimal. E~amples of neutral proteases include Milezym~ (a~ailable from Miles Laboratory) and trypsin9 a naturall~ occurring protease. Alkaline proteases are available from a wide ~ar;ety of sources, and are typically produced from various microorganisms ~e.g., Ba~illis .s~ktilisis).
Typical e~amples of alkaline proteases include Ma~atase and Ma~acal from International RioSynthetics, Alcalase, Savinase and Esperase, all available from Novo Industri A~S. See also Stanislowski e~ al., U.S. 4,511,490.

Further sui~able enzymes are amylases, which are carbohydrate-hydrolyzing enzymes. It is also preferred to include mi~tures of amylases and proteases. Suitable amylases include Rapidase, ~rom Société Rapidase, Milezyme from Miles ~ahoratory, and Ma~amyl from International siosynthetics.
Still other suitable enzymes are cellulases, such as those described in Tai, u.S. 4,479,881, Murata et al., U.s. 4,443,35~, Barbesgaard et al., U.S. 4,435,307, and Oh~a et al., u.S~
3,933,082.
Yet other suitable enzymes are lipases, such as those des.ribed in Silver, U.S. 3,950,277, and Thom et al., U.S.
4,707,2910 The hydroly~ic enzyme should be present in an amount of about 0.~1-5%, more preferably about 0.01-3%, and most preferably about 0.1-2% by weight of the detergent~ Mi~tures of any of the foregoing hydrolases are desirable, especially protease/amylase blends~
Additionally, optional adjuncts include dyes, such as Monastral blue and anthraquinone dyes (such as those described in Zielske, U.S1 4,661,2g3, and U.S. 49745,461).
Pigments, which are also suitable colorants, can be selected, 3~ without limitation, from titanium dio~ide, ul~ramarine blue ~see also, Chang et al., U.S. 4,708,816), and colored aluminosilicates.

. " ~

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, ~ ,; ;: - . :

1 3 2 ~
Fluorescent whitening agents are still other desirable adjuncts. These include the stilbene, styrene, and naphthalene derivatives, which upon b~;ng impinged by ultraviolet light, emit or fluoresce light in the visible wavelength. These FWA's or brighteners are useful for improving the appearance of fabrics which have become dingy through repeated soilings and washings.
Preferred FWA's are Tinopal*SBMX-C and Tinopal*RBS, both from Ciba Geigy A.G., and Phorwite*RXH, from ~obay Chemicals. E~amples of suitable FWA's can be found in U.S. Patents 1,29R,577, 2,076,011, ~0 2,026,054, 2,026,56S, i,393,042; and U.S. Patents 3,951,960, 4,298,290, 3,993,659, 3,~80,713 and 3,627,75~

Anti-redeposition agents, such as carbo~ymethylcellulose, are potentially desirable. Nest, foam boosters, such as appropriate anionic surfactants, may be appropriate for inclusion herein.
Also, in the case of e~cess foaming resulting from the use of certain surfactants, anti-foaming 3gents, such as alkylated polys7lo~anes, e.g., dimethylpolysilo~ane, would be desirable.
Fragrances are also desirable adjuncts in these compositions, 20 , although the activators herein have much lower o~or than the fatty acid esters such as those in Chung ~t al., U.S. 4,412,934.
The additives may be present in amounts ranging rom 0-50%, more preferably 0 30%, and most pxeferably 0-10%. In certain cases, some of the individual adjuncts may overlap in other ~5 ~ategories. However~ the present invention contemplates ea~h of the adjuncts as providing discrete performance be~efits in their various categories. The EXPERIMENT~L section below demonstrates the advantages o the inventive bleach activator~ and the deterqents containing them.
~Trade Mark .....
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~1 32~8 TA~LE I~
~leach Activator Granules omPon~

gO Precursor 2.5 ~ 8inder, C16_18 ethoYylated alcohol (Alfonic 1618-80 from ~l~ta Ch~mical Co.).

2.5 ainder, C12 sodium alkyl aryl sulfonate (Calsoft L40 from Pilo-Chemical Co.) t 0~ an actives ~2S_S .

Diluent, can be any inert salt s-~ch as Na~S04, Na~CO3, NaCl, etc.

Deterg~nt Formulation -C~ ~
~: ~a Tripolyphosphate 33.21 ELAS 11.29 : 30 ~a Perborat~ Monohydrate7.46 2C3 40.~0 Silicate 4.98 oisture 2.k6 ~ 100.00 : 35 :
.

~32~8 _TAI/L~ VI
Detergent ~ Activator Formulation Component wt.%
Na Tripolyphosphate 27.16 HLAS (Biosoft S130) 9.23 Na Perborate Monohydrate6.10 ` Na2C3 33.04 1~ Silicate 4.07 Activator Granule-~ 8.94 Na2S4 6.74 Alcospersel 0.32 Ultramarine Blue ~ 0.15 l; FWA3 0.32 Dequest 20064 0.50 Savinase5 0.91 : Fragrance 0.20 Moisture - 2.32 100.00 ~; :
Polyacrylic Acid Binder, Alco Company.
3 Colorant.
F}uorescent whitening agent.
,~ 4 Chelating agent, Monsanto CompanyO
Protease enzyme, Novo Industri ~/5.

~: 30 : 3 ~ 3 ~

Solubility and Crush Durabllity The results in TABLE VII show the solubility index and crush durability for several noodle compositions. The solubility index is defined as the time in minutes required for a 0.2 9 sample to completely dissolve in 500 mL water at about 21C under constant stirring to yield a 2cm vortex in a 1 liter beaker. The crush durability factor is the weight in grams required to crush a 2mm (length) granule between glass plates.
TAsL~ VII
Granules nd Their Solubility Tndex_and Crush Durability Binder ~Activator ~Binder %3iluent Solubility Crush Factor (Mins.)(in grams) Alfonicl 302 10 0 5.23 40 1618-80 852 15 0 3.88 63 80~ 20 0 3.75 81 802 15 5 3.4 55 Calsoft F9o31002 0 0 10.0 ~40 902 10 0 2.1 40 852 15 0 1.5 40 802 20 0 2.0 40 50/50 ~lend 90~ 5 5 3.0 111 Calso~t L404 50/50 Blend 906 5 5 3.5 76 Alfonicl 1618-80/Calsoft 1 Nonionic surfactant, Vista Chemical Company.
~ Activator is sodium octanoyloxyacetate, phenol sulfonate ester.
3 Anionic surfactant, Pilot Chemical Company, 9o% active.
4 Anionic surfactant, Pilot Chemical Company, 40% active.
5 Polyethylene glycol (M.Wt a4,600), Union Carbide.
6 Activator is sodium nonanoyloxyacetate, phenol sulfonate ester.

. . ., ,~ ,, ~ .

1 3 2 ~

P~h~Qlysis and Storaq~ Sta~ Y
The ollowing granular dry bleaching compositions were prepared:

çç~EQnçn~ inLgL~ms Na Perborate Monohydrate 0.175 g t~8 ppm ~.O.
~a2~3 1.200`g Acti~ator gram amount equivalent to 14 ppm A.O.
~via granule or theoretical powder) The perhydrolysis profiles of the above bleach compositions (see TABLE IX, below) we~e carried out in the prese~ce of Tide~
lS (Procter & Gamble Com~any) deterqent. The composition (appro~imate) of this detergent is shown below in TA8LE ~III.

TABLE VIII
Composition of Tide~ Detergent ~om onent Wt.
~a2CO3 14.7 ~a Tripolyphosphate 37.9 E~a2O~si~2 4.0 ~a LAS 4.0 ~a AEOS 13.0 Ti~opal AMS ~brightener) 0.21 Water ~moisture) 5.5 ~a2SO4 ~Q.~ _ 100 . 00%
Although this parSicular detergent base is used, sther anionic or non;onic based detergents could be utilized as w~ll.
The active oxygen profiles were obtained in the following manner: The bleachi~g compositions were placed in 1,000 m~ water .: . -~ . . . ~ : : .

~. ~L 3 ~
~ - 41 -at 21.7C, at 100 ppm hardness (3/1 Ca+2/Mg+2), 1.5 mMol.
NaHC03, with the detergent content at 1.287 g/L. The solution pH was adjusted to 1005. The water was stirred at a rate so ~s to yi~ld a 3cm vortex, in a standard 2 liter beaker, a~d the amount S o~ active o~ygen (AØ) from peracid generated was determined iodometrically.
The results are shown in TABLE IX below, which demonstrate the benefit of us;ng a granulated activator over the powdered actlvator, which was claimed in U.S. Patent 4,778,618. The granulated activator disperses more rapidly than the powdered activator, thus yielding a higher active oxygen level over a longer period of time.

T.~B~E IX
Perhydrolysis Profile of Granulated v~r~us Powd~e~ ~ctivat~r__ ~ample % A.Q. of.th~oreti~al @ various~imes tminutesL
t-2 t=~ t=12 Granulel 93 84 Bl Powder2 45 71 82 1 Granule was octanoyloxyacetate, phenol sulfonate ester, 90%, with linear Cll.s alkylbenzene sulfonate, sodium salt, 10~
2 Powder was 100% octanoylo~yacetate, phenol sulfonate ester.
Storage stability of dry bleach compositions containing the activator were determined under the following conditions: The compositions were placed in open glass vials and stored in a storage room which maintained a constant temperature of about 32C
and a relative humidity of about 85%. After storage, the samples were measured for their activator content by determining the yield o~ peracid A.O. in solution at si~ and twelve m;nutes.

The percent activator of various samples after storage are sh~wn in TABLE X.

;

:: - . -: -- 4 ~ 3 ~

TABLE x Storage S~abili~y in Open Glass Vials 32C, 85% relative humidity Sample % of original A~O, remaining S ' ~ _ 7 ~
~ct va~orl/ 100 100 7g 66 LAS~, 90/10 Activa~o~ 100 76 9 5 (Powder) 1~

Octanoyloxyacetate, pnenol sulfonate ester.
2 linear Cll,s alkyl ~enzene sulfonate.

The resul~s in TAB~ X show that granulated activator is significantly more storage stable than the powdered ac~ivatox.
After ten days storageD the granules exhibit a ~4~ A.O. loss, wnile the powder experiences about 95~ A.O. loss.

~: : In the test below, storage stability of the noodled/gra~ulated activator was compared against the powdered activator. The conditions were: 37C, 70% relative humidity stored in an anionic (phospha~e~ base ~see, e.g~, the formulation of ~ABLE VI~ above).
~he granules contained 90~ nonanoyloxyacetate, phenol sulfonate ~: ~ ester; 5% Na2SO4, and ~% binder ~LAS and Carbowax 8000, ;~ Car~owax 4600t Alfoni~ 1618-80, each at 50/50 wt./wt.).
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~ 30 ~:

~ 35 :

. ~ ....... . , . . . : . .. . .. ..

~ . . .. . ,, .,; - ~ . . . ..

~32~8 TABLE XI
~ A.O. yield of theoretical Binder ~=0 ~=1 week t=2 weeks Carbowax 8000/LAS1 88% 83% 73~
Carbowax 4600/LAS1 88~ 83% 73%
Al~onic 83~ 80~ 73%
1618-80/LASl .
Powdered 63~ 25% 0 Activator ~LAS = Calsoft L40, Pilot Chemical Co.

Further tests were conducted comparing the granulated/noodled activator against the powdered activator, but this time, as a detergent composition. In thîs case, the activator evaluated was nonanoyloxyacetate, phenol sulfonate ester. The data were obtained in the presence of the detergent formulation of TABLE V
above. 1.4g of the detergent was added to 1,000 mL of water at 21C in a 2 liter beaker and stirred at a rate so as to yield a 3 c~ vortex. The results are reported below, in TABL~ XII.

:

1~
, l,~ 35 . ~ .

~L32~$

TA~L~ X~I
Perhydsolysis Profil~ of ~oodled Activator ~ersus Powdered Acti~ator fi~m~ A.O. of theoretical at ariQus ~imes ~t~ in d~YS_ t54 t-8 t=12 Activatorl~8 8B 78 ~cti~ator262 66 56 ~Powder) TO

l~onanoylos~acet~te, p~enol sulfonate ester, 90% (as produced~, granulated with Calsoft L40r 2.5~, PE~ 4600, 2.5%, sodium sulfa~2 ~filler), 5%.
~onanoylo~yacetate, pbenol sul onate ester, 100% (as produced).

Further experiments conducted tested the performance of ~; particular surfactan~s in the detergent base with which the activator granules were combined. Surprisingly, Applicants : 20 discovered that perfor~ances of certain long chain linear alkyl : benzene sulfonates demo~strably improved cleaning performance.

Chain length Distributions:
L~ Ql~ Wt.
: : 1. Biosoft S130 ~ 17% 50% 2~ 340 2. Biosoft ~100 20% 43% 32~ 4% 1% 316 .
~ A nonphosphate detesgent ha~i~g the formulatio~ as i~ TA~LE
~rY below used surfac~a~ts ~ a~d 2 shown in T~BLE XIII in the detergent bas~. These two esamples were teste~ in wash wat~r at about 21~C, lOQ ppm har~ess and the results reported i~ TABLE

~5 ~ `

- 3L 3 2 ~ 5 ~ ~

~A~I.E XI~
~o~phosphalte r~tergent + A~ ivator Formulation ~s2mPonent wt ~
~a2C03 61. 13 ~ILAS 11 . 34 Na Perborat~ ~onohydrate 7.49 Silicate 6.48 ~ctivator ~ooal~ 9 . 97 Minors, includi~g Na2SO4 U~IB, Enzyme, ~sture, e~c.~,~
100.00 Th~ ollo~i~g ~rformance dat~ wese ther~y obtained:

T~BI,E XV
Perormance ComparisoDL
~oi 1 Removal~E~
S~bum on Sebum on Sebum on ~ Cottorl PolYes~er PolYcot~on Biosoft S130 71.9 92.6 81.6 Biosof t S100 62 . 2 73 . 8 69 .1 LSD t-tes'Ç 7.6 3O9 9.8 25 (95~ confl~e~ce) ~vera~e ~c~res l~o~ .R. on_~ll Fabrics ~iosoft S130 82 . 0 Biosoft SlOû 68.4 LSD t-tes~L 4 4 ( 9 5~ conf 1 e~ce~

~: ' ' ' ' ' ' ' ' ' ' ~ '' ' ' :

~324~58 The above data demonstrate that selection of surfactant can have a significant effect on performance in detergent compositions containing the inventive activator granules. Thus~ it has been shown that longer chain anionic sufactants are especially desirable for implementation in Applicants' detergent systems.

In another test, the effect on perfotmance is reviewed when sodium perborate tetrahydrate is used as the oxidant7 the surfactant chain length is varied, and the builder system is non-phosphate. The formulation in TA8LE XIV, above, was used, with conditions o~: perborate tetrahydrate crystals with particle size of U.S. mesh grade 30; 21C, 100 pp~ water hardnesaJ and nonphosphate builder system (DH 10-10.5).
L_ The results are shown in TABL2 XVI.

TAaLE XVI
~ A.O. of peroxide yield at 12 minutes Surfactant ~ Per 203ioso~t S130 31% 95 ~iosoft S100 91~ 95%
Neodol 25-9 95~ 95 l Sodium perborate tetrahydrate.
2 Sodium perborate m~nohydrate.

The above results demonstrate that in a non-phosphate system, the chain length of the surfactant can influence solubility of the perborate tetrahydrate, when the surfactant is anionic. Further, the e~fect is not influenced by pH in the 9.8 - 11.0 range, water hardness (0-200ppm), and temperature below 32~C.
Because o~ this effect, it is preferred to use perborate monohydra~e in a non-phospha~e system which, as shown in TABLE
XVI, is soluble.

~r ~ ,, ~ ~ .

. . , - -- ~ , . - . ~ .- . , ~ ;

` 132~SS~ -In yet another test below~ the solubility difference between the phosphate detergent for~.ulation contai~ing sodium perborate monohydrate in TABL~ VI and an identical foraulati~n containing sodium perborate tetrahydrate were compare~. The amount of particulate residue collected on a black s~atch after filtering the wash solution therethrough indicates the degree of solubili~y of the respective formulations.
The procedure for determining detergen~ residue (mean~ to simulate scaled-down misuse conditions) is as follows: lOg detergent i~ added to a 2 liter beaker ~on~aining l,OOOmL water at about 21~C and stirred at a rate so as to yield a vortex of about 2-3 cm. After a time of ten minutes, the solution is filtered o~to a black cloth (which has bee~ previously weighed). The cloth and the undissolved pa-ticle~ are collected and dried. The dried cloth is then re-weig~ed to determine the amount of undissolved particles.

TABLE XVII
Detergent Solubilit~
Exam~le Al O . 011 B2 0.293 Detergent formula describ~d in TABL~ VI, above.
2Detergent formula listed in TABLE VI, with sodium perborate tetrahydrate substi~uted for sodium per~orate monohydrate.

.. . .
,: -. :, . ~ :

" , . ~ . ,~ .. , .. ., .. . ~ . ;

1 3 ~
-- 4~ --The above test results reported in TABLE XVII demonstrate that when the surfactant used is C~12 14 HLAS, in a no~-phosphate system, it is preferred to use perborate mo~ohydrate as the peroside source i~ order to reduce residual undissolved particles.

The nest e~periments show the effect of heavy metal ions on solution stability of the in situ formed peracid from the inventive activator granules. Surprisingly, the use of an 1~ amino-polyphosphonate chelating agent reduce~ loss of peracid formed in solution whe~ hea~y metal cations were pres~nt.
Tri(methylene phosphonic acid) amine (Dequest 2000 manufac~ured by ~onsanto) was used as the chela~ing agent. Its effect on peracid decomposition in the presence o~ Cu~+ ion was me~sured 1 by dissolving 4.5g o the detergent ~omposition shown in TA3LE
VI into three liters o~ water co~aining 100 ppm hardness ~3:1 Ca~2:Mq~2) ànd the concentration of copper shown in Table XVIII. The composition co~tained nonanoylosyacetate phenol sulfonate ester as a powder.

~
TA~hE XvILI

Average ppml of A~0. 4, 8, and 12 minutes 2~ E~mPle ~va. ~ AlQ ~ ~Pml ~quç~t 200 1 . 2.7 o 2 2.0 50 0 3 1.3 100 4 0~9 250 0 3~ 5 2.6 250 10 1 ppm z part~ per million.2 ppb e part~ per billion.
Table XYIII clearly demonstrates that heavy metal cations, 3~ e.g., copper ion, decompose the peracid formed from the act;vator and that a chelating agent (Dequest~ 2000) pre~ents this ~opper ion catalyzed decompo~ition.

- ~L32~;5~8 o ~9 The invention ic further e:~emplified in the Claims whic:h follow. Howe~rer, th~ invention is not limited thereby, and obvious embodiments and equi~alents thereof are within the clalmed invention.
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Claims (32)

1. Stable bleach activator granules comprising:
a) a peroxygen bleach activator having the structure:

, wherein R is C1-20 branched or straight chain alkyl, alkoxylated alkyl, cycloalkyl, alkenyl, aryl, substituted aryl, alkylaryl; R' and R" are independently H, C1-4 alkyl, aryl; and L is a leaving group;
b) a pliable binding material selected from materials having a melting completion temperature of greater than about 40°C.

2. The bleach activator granules of claim 1 which additionally comprise c) a filler material.

3. The bleach activator granules of claim 2 wherein the proportions of a:b:c range from about 99:0.5:0 to about 50:25:25.

4. The bleach activator granules of claims 1 or 2 wherein the activator of a) has a leaving group, L, the conjugate acid whereof has a pKa of about 4 to 20.

5. The bleach activator granules of claims 1 or 2 wherein the pliable binding material of b) is selected from the group consisting of anionic surfactants, nonionic surfactants, water soluble organic polymers, water dispersible organic polymers, and mixtures thereof.

6. The bleach activator granules of claim 2 wherein the filler material of c) is an inorganic or organic filler.

7. The bleach activator granules of claim 6 wherein the filler material is an inorganic filler selected from alkali metal and alkaline earth sulfates and chlorides.

8. The bleach activator granules of claims 1 or 2 wherein the activator has a leaving group, L, is selected from the group consisting of :

( i) , wherein Y and Z are individually H, SO3M, CO2M, SO4M, OH, halo substituent, OR1, R2, NR?X, and mixtures thereof, wherein is an alkali metal or alkaline earth metal counterion, R1 of OR1 is C1-20 alkyl, R2 is C1-6 alkyl, R3 of NR? is C1-30 alkyl and X is a counterpart ion thereto, and Y and Z can be the same or different;
( ii) halide;
(iii) -ONR4, wherein R4 contains at least one carbon which is singly or doubly bonded directly to N;

( iv) , wherein R5 is a C1-10 alkyl; and ( v) mixtures thereof.

9. The bleach activator granules of claims 1 or 2 wherein the activator has the structure , , or , wherein R is C1-20 alkyl, and L is a leaving group selected from the group consisting essentially of substituted phenol, oxime, amine oxide, and oxyimide.

10. The bleach activator granules of claim 9 wherein the precursor has the structure , and Y and Z are separately selected from H, SO3M, CO2M, SO4M, OH, halo substituent, OR1, R2, NR?X, and mixtures thereof, wherein M is an alkali metal or alkaline earth metal counterion, R1 of OR1 is C1-20 alkyl, R2 is C1-6 alkyl, R3 of NR? is C1-20 alkyl, and X is a counterpart ion thereto, and Y and X can be the same or different.

11. The activator of claim 10 wherein the precursor has the structure:
.

12. The activator of claim 11 wherein the precursor has the structure .

13. The activator of claim 11 wherein the precursor has the structure .

14. The activator of claim 11 wherein the precursor has the structure .

15. The activator of claim 11 wherein the precursor has the structure .

16. The activator of claim 11 wherein the precursor has the structure .

17. The activator of claim 11 wherein the precursor has the structure .

18. The bleach activator granules of claims 1 or 2 further comprising d) a bleach-effective amount of a source of hydrogen peroxide.

19. The bleach activator granules of claim 18 wherein said source of hydrogen peroxide is selected from the group consisting of alkali metal perborates, alkali metal percarbonates, hydrogen peroxide adducts and mixtures thereof.

20. Stable bleach activator granules comprising:
a) a peroxygen bleach activator having the structure:

, wherein R is C1-20 branched or straight chain alkyl, cycloalkyl, alkenyl, aryl, alkylaryl; R' and R" are independently H, C1-4 alkyl; and L
is a leaving group;

b) an organic binding material;
wherein said granules are approximately cylindrical or spherical, and have a diameter of about 25 to 2,000 microns, and dissolve, in water, within about 10 minutes at 21°C.

21. The bleach activator granules of claim 20 wherein said binder of b) is an organic material.

22. The bleach activator granules of claim 21 wherein said organic material is selected from the group consisting of anionic surfactants, nonionic surfactants, water soluble organic polymers, water dispersible organic polymers, and mixtures thereof.

23. An activated oxidant detergent comprising:
a) bleach activator granules comprising:
i) a peroxygen bleach activator having the structure:

, wherein R is C1-20 branched or straight chain alkyl, cycloalkyl, alkenyl, aryl, alkylaryl; R' and R" are independently H, C1-4 alkyl; and L
is a leaving group;
ii) a pliable binding material selected from materials having a melting completion temperature of greater than about 40°C;

b) a detergent base which comprises:
i) builders;
ii) fillers;
iii) a surfactant selected from the group consisting of anionic, nonionic, cationic, amphoteric, zwitterionic surfactants, and mixtures thereof;
and c) a bleach-effective amount of a source of hydrogen peroxide, which acts in combination with the activator granules of a).

24. The activated oxidant detergent of claim 23 wherein the bleach activator granules additionally comprise a)iii) a filler material.

25. The activated oxidant detergent of claims 23 or 24 further comprising d) a detergent adjunct selected from the group consisting of enzymes, dyes, pigments, fluorescent whitening agents, anti-redeposition agents, anti-foaming agents, buffers, fragrances, and mixtures thereof.

26. The activated oxidant detergent of claims 23 or 24 wherein said surfactant of b)iii) is a nonionic surfactant, an anionic surfactant, or a mixture thereof.

27. The activated oxidant detergent of claim 26 wherein said surfactant of b)iii) is an anionic surfactant selected from the group consisting of sulfonated aromatic surfactants.

28. The activated oxidant detergent of claim 27 wherein said surfactant is a C 6-18 linear alkylbenzene sulfonate.

29. The activated oxidant detergent of claim 28 wherein said surfactant is a C12-14 linear alkylbenzene sulfonate.

30. The activated oxidant detergent of claims 23 or 24 further comprising a chelating agent.

31. The activated oxidant detergent of claim 30 wherein said chelating agent is selected from aminopolyphosphonates, polyphosphonates, ethylenediaminetetraacetic acid, and mixtures thereof.

32. The activated oxidant detergent of claim 31 wherein said chelating agent is an aminopolyphosphonate.