CA1234326A - Bodies containing stabilized bleach activators - Google Patents

Abstract

BODIES CONTAINING STABILIZED BLEACH ACTIVATORS
ABSTRACT OF THE DISCLOSURE
The invention relates to bodies containing bleach activators.
The bodies comprise specific peroxygen bleach activators and select binder or enrobing materials. When formulated in such bodies the peroxygen bleach activators have excellent storage stability and maintain excellent dispersibility in wash water.

Description

:~23~32~

PEROXYGEN BLEACH ACTIVATORS AND BLEACHING COMPQSI~IONS
James F Thompson Charles D. Broaddus TECHNICAL FIELD
This invention relates to novel compounds and compositions useful in peroxygen bleaching. More parkicul~rly, this ~nventisn - relates to novel peroxygen bleach act~vator compounds that aid in provid;ng effective and efficient peroxygen bleaching of textiles over a wide range of temperatures and conditions.
This invention also relates to bleach~ng detergent compositions employing these peroxygen bleach activator compounds in combination with a peroxygen bleachlng compound capable of yielding hydrogen peroxide in solution. In a highly preferred embodiment the bleaching compositions of the present invention are stable detergent compositions. This invention further relates to methods of making the peroxygen bleach activator compounds.
Lastly, this invention relates to particularly stable bodies containing these peroxygen bleach activator compounds in combination with certain binder or enrobing compounds.
It is well known that peroxygen bleaches are effect1ve in removing stains and/or soils, as well as vlsible evidence of stains and/or soils, from textiles. Unlike sodium hypochlorite bleaching solutions, they can be readily employed in a variety of bleachlng and detergent compositions. However, the efficacy of - 25 peroxygen bleaches can vary greatly with temperature. These ; bleaches are only practicable and/or effective when the bleaching solution (bleach and water mixturej is above about 60C. When employed in a bleach solution at a ~emperature of about 60C or below, peroxygen bleaches are significantly less efficacious than at higher temperatures . Thereforeg in order to obtain a des~rable level of bleach~ng performance at these lower te~-peratures, extremely high levels of peroxygen bleach mus~ be employed. Due to the cost of peroxygen bleach compounds, levels necessary to achieve good bleaching performince at such temperatures are economically ~mpracticable. In ble~ch solutions ,:
:.

~ ~ .
,~ .

~ 3 ~ 3~6 where the temperature is well below 60QC, peroxygen bleaches are rendered almost totatly ineffective regardless of the level of pero~ygen bleach compound added to the system.
The dependence of peroxygen bleach perfor~ance on temperature (and concentration), described above, is both practically and economically significant. Peroxygen bleaches are most co~monly used as detergent adjuvants in home laundry products. Thus, the typical textile wash process employing these bleaches utilizes an automatic household washing machine and a wash-water temperature below 60C. (The low wash-water temperature utilized reflects concern for both textile care and energy consumption.) As a consequence, there has been much interest in developing substances that would increase the efficacy of peroxygen bleach compounds allowing them to be effectively employed at a temperature below 15 60Co Such substances are generally re~erred to in the art as bleach activators or peroxygen bleach activators.
8ACKGROUND OF THE IN~ENTION
Numerous substances have been disclosed in the art as effec-tive peroxygen bleach activators. A~ong the best known of these are the substituted and unsubstituted carboxylic acid ester bleach activators~
U.S. Patent 3,130,165, Brocklehurst, issued April 21~ 1964, describes a household laundry detergent composition. This compo-sition contains a detergent, from 3-20~ by weight of an inorganic 2s peroxy-compound, and from about 0.5 to about 2.S ~oles of a phenol (or substituted phenol~ ester o~ alpha-chloro-acetic or -propionic acid per mole of available oxygen.
~ , July, 1967, describes chloroacetyl salicylic acid as an activator for low temperature perborate/peroxide bleaching.
U.S. Patent 3~075,921, ~rocklehurst, et al., issued January 29, 1963, discloses 2-chloro, 4-chloro, and 2-methoxy peroxyben-zoic acid. These acids are described as pro~iding excellent bleaching activity when incorporated into solid detergent compo-sitions.
British Patent Specification 864,798 9 published April 6,1961, discloses bleaching composi~ions eomprising an inorganic , ..

23~3Z6 pers~lt comb~ned w1th lln organlc ~ster of an ~11ph~tlc c3rboxyllc actd. The ~ddltton of t~ese esters to the ~5h ~o'~10n ~s s~1d 1;o g~ve ~ @are Ylgorous bleachlny ~ct10n th~n the h~drogen per-ox~de ~lone. Such ~ system therefDre penn~ts lo~-temper~ture bleach1ng (5~60C) under o~herw~se nonn~ shlllg conditîons. It ~s preferred th~t the ester be der~ved frqm ~n ~1 ~ph11t~c s~r ~oxyl~c ~t~d h~v1ng not ~ore th~n 10, ~nd preferably less th~n 80 carbon ~tolns. The patentee states thl~t such ble~ch~ng ccmpos~-t~ons ~re st~ble durlng stor~ge.
Br~t1sh Patent Speç1f~cat10n 836,~8, publ~shed June 9, 1960, descrlbes bleach~ng and detergent oomposlt~ons contlllnlng an ~norgan~c pers~llt and ~n organ~c carboxyltc acld esterO It 15 a~lleged that such esters prov~de ~mproved bleach~ng at tempera-tures between 50 to 60C ~hen compared to systems employing the pers~lt alone. Spectflc examples ~nclude sod~um dodecyl benzene sul~onate ~nd sodium dodecyl phenyl acet~Se.
It ls ~lso known th~t bleach ~ct~vators khich exh1b~t surface ~ct1v~ty can be used ln combinat~on wlth peroxygen-type ble~ches : to proYide part1cularly effect1ve s~rf~ce ble~ch ~9. U.S. P~tent 4~283,~01, D~ehl, ~ssued August 11~ 1981, dlscloses bleach~ng compos1t10ns compr~slng a peroxygen bleach, such as pers~lt, and ~
ble~ch ~ct1v~tor. ~he ~ctlvators descr~bed ~re esters of e~ther ~n alkyl oono- or d~-c~rboxyllc ~o1d. These actlYators ~ay be represented by the general fonmul~:
R-~-Z or Z-~-R2~-Z

~herein R ~s an ~lk~l ch~n containing ~m ~bout 5 to ~bou$ 13 carbon ~toms, R2 is an ~lkyl ch~n containing from about 4 to ~bout 24 carbon ~toms, and Z ~s ~ leav~ng group. The patentee states th~t the selected bleach and ble~ch actlv~tor 3re preferably present ln equ~molar rat~os.
~ .S. P~tent 4,412,934, Chung, et ~l., disclbses ble~ch~ng compos1tions containing a peroxygen bleachlng compw nd and bleach ~ct~v~tor of the ~eneral ~onmwlao i23~326 ~ 4 -L
~here~n R ~s an ~lkyl group cont~ln1ng ~ bout 5 to obout 18 carbon at~ms w~th the longest l~near ~lkyl chaln be~ng ~rs~ ~bout 5 6 to about lO carbon ~to~ns; L ls a leavlng ~roup. It 1s further requlred th~t the ton~ugate ~c~d of the ~ct~Yator oust h~ve a pK"
~n the range of fr~ about 6 to about 30. The ~lar r~t~o of the hydrogen perox~de gener~ted:~ctlYatoY ~3ust be ~reater th~n ~bout ~5:1 .
Certa~n benzene sulphonate compounds ~ith ~n ~lkoxy group subst~tuted on the r~ng are kno~m to be usefJl 1n elean~ng com-pos~t~ons. U.S. 3,685,127, Boldlngh, et ~l., 1ssued August 22~
1972, descr~bes detergent composlt~ons ~îth ~proved bleach~ng c~pab~l~ty contalnlng (l) ~n lnorgdnlc persalt" (21 ~n org~ln1c 15 detergent and (3) a bleach precursor hav1ng tlhe gener~l fo~ula:
~CO~
X~5~3M

~ ere~n X is ~ br~nched or str~llght ehaln alk~rl or ~lk~nDyl 20 r~dlc~l cont~inlng 6 to 17 carbon i~toms, ~ lls hydrogen or ~n alkyl rad~cal h~vllng 1 to 7 carbon atoms, and Pl ls an ~lkal~ ~*tal or an~non~um r3d~c~1. Spray-dried detergent colnpos~t~ons cont~in~lng

2-acetoxy-5-nonyl benzene sulfonate are d1sclosed.
Certaln ~lpha-chloro and ~lpha-alkoxy ~cld esters ~re known 25 to be useful ~s perfumes ln cle~ning compos1t~ons. For example~
ll.S. Patent 3,368,943, 6ilbert, ~ssued February 13, 1968, dis-closes compounds of the fonnula:
:~ H3 H
RO - _ C - COOR ' 3n - H3 X a k~herein a ~s O or l; X îs chlor~m r ~romlneD R ~s 0ethyl or ethyl; and R' 15 ~I saturated C4-C12 al~phatio branched or 11ne~r ch~ln, benzyl, phenol ethyl, or phenol propyl rad~cal. ~he compounds descrlbed ~y the p~tentee are sald to possess an 35 ~greeabl2 odor. These eompounds lnelude ~lpha-slko3~y ~sobutyra~es and alph~-ha10 bgta-21ko%y lsov~lerates. ~s perfun#s, these .
"~"

'~3~3'~6 c~npounds 3re s~1d to be parSlcul~rly ~u1tabl~ for use in ~etergents ~nd ~bleach~ng a1d" compos1t10ns. Cllean~ng eom-pos~t1nns ~ ~etergent co~npos~t~ons, ~nd !~ar s~lp CO~IpOS~t~ons perfumed w1th these comp~unds are d~selosed.
Poly-~lph~chloro 3l~cryllc aDtld ls d~stlosed ~n the art a~
~e~ng useful in detergent compos~t1cnt ll5 l~oth ~n ox~di2~ng ~gent and ~s a th1ckener. I~r~t~sh Patent Spec~fic~t10n l7420,468, published 3anuary 7, 1976, suggests th~t oxld~ng ~gents c3n be ~ener~ted ~n a wash solution ~f he or~g~n~l detergent compos~t~ons cont~ln ~ com~n~t~on of sodium perborate and a poly-alpha-hydroxy acryl~e ac~d, ~ poly-~lpha-chloro acryl~c ~c~d~, or aD der~v~t1ve of these compounds.
U.S. ~atent 3,553,l40, McCrudden, ~ssued May lS, 197~, discl~ses cert~n carboxyl-groupDcont~n~ng pol~mers useful ~s thlckeners in detergent eompos1t~ons ~h~ch add~t~onfilly eontain a perborate. Alph~-chloro acrylic ac~d 1n a detergent compos~tion ~s speci~1cally disclosed.
U.S. Patent 3,969,257, Murray, ~ssued ~uly 13, 1976, suggests that acetyl s~licyl1e ac1d ~s useful ~s an act~vator for soluble peroxide bleachlng agents ~n detergent compos1t~ons.
~h~le the o~erall efflcacy of c~rboxyl~c ~c~d ester ble~ch ; octivdt~rs ~ost s~m~lar to those of the present lnvention is unquest~oned, these ~rt-distlosed compounds ~ost slm~lar to those of the present ~n~ent10n suffer ~rom one s~gn~icant dr~wback:
. 25 they yleld compounds ~the act~ve component) bh kh ~ossess a part~cularly repugnant odor under ~ctual us~ge cond~t~ons ~pH, temperature, etc.). Because they possess this odor under ~c~u~l ~ash cond1tions, thelr overall ut~llty ~nd v~lue ~s grea~ly reduced.
The m~lodor ~ssoc~ated w~th these cQmpounds (the ~ctive component) ~s ~ell-known ~n the Art. See ~Organlc Perox1des And Peroxy Compounds~, K~rk-Othmer Enc~cloped~a of Chem~c~l_ Tech 7, 6~.
U~S. P~ltent 4,009,113, 6reen, et ~ ssued February 2~, ': 35 1977, d~scloses ~ranular conpos~t~ons compr~s~ng from ~bout 40X to ~bout BOX of ~ bleach actiY~tor and an ~nert oarr~er ~er~al such ~1 2343~6 as long chain fatty acids or esters wherein said precursor is substantially evenly distributed with said precursor compound to form a composite particle. The particle has an outer protective layer which can consist of, for exam-ple, polyvinyl alcohol. It is stated that such composi-tions have both good storage stability and dispersibility in the wash water.
U.S. Patent 4,399,049, Gray, et al., issued August 16, 1983, discloses a detergent additive composition compris-ing from about 75% to about g5% of a particulate infusiblesolid having a particle size distribution such that at least about 50% thereof passes a 250 micrometer screen and comprising storage sensitive detergent additive materials, and from about 5% to about 25% of ethoxylated nonionic surfactants melting in the range of from about 20C to about 60C wherein said composition is prepared via a radial extrusion process. It is stated that such compo-sitions haYe impro~ed storage stability together with excellent release and dispersibility characteristics in wash water.
Japanese OPI Publn. No. 59-135299, Chung, published August 3, 1984, describes stable compositions employing binder and enrobing materials similar to those of the present invention. These compositions contain 4-(alka-noyloxo)benzenesulfonates.
It has now been discovered that certain alpha sub-stituted derivatives of the C6-C18 carboxylic acid esters provide particularly effective peroxygen surface bleach-ing performance but do so without generating the malodor associated with the use of corresponding unsubstituted or shorter chain (art-disclosed) compounds.
It has also been discovered that these alpha substi-tuted C6-C18 carboxylic acid esters, while very reactive, can be stabilized for storage by forming bodies containing the esters and select binder or enrobing materials, such as sorbitan esters.
It has further been discovered that these alpha sub-stituted C6-Cl~ carboxylic acid esters can be simply prepared under anhydrous conditions without generating noxious products.

r~

SUMMARY OF THE INVENTION
The present invention comprises a body containing bleach activators comprising:
(a) from about 50% to about 98% of a bleach activator compound of the general formula R - ~ - C - L

where R is a straight or branched alkyl or alkenyl group having 10from about 4 to about 14 carbon atoms, R1 is H or C2H5, X is Cl, OCH3 or OC2H5 and L is a leaving group selected from ~ R Y
- ~ , - O ~ Y and - O ~
wherein R i5 an alkyl chain containing from about 1 to about 8 carbon atoms, and Y is -S03 M or COO M wherein M is sodium or potassium; and (b) from about 2% to about 50~ of a binder material selected from the group consisting of nonionic surfactants, polyethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereof, wherein said binder does not melt below about 40C; and wherein (a) and (b) are substantially evenly distributed throughout said body, the density of said body is above about 1.06 g/cc and said body contains less than about 5%
water. Preferred binder or enrobing materials include sorbitan ; 25 monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, or mixtures of these compounds.
Further, the present invention comprises peroxygen bleach activator compounds of the general formula x~ e 30R - ~ - C - L
Rl wherein R is a straight or branched alkyl or alkenyl group having ; from about 4 to about 14 carbon atoms, R1 is H, CH3, C2H5, or C3H7, X' is Cl, OCH3, or OC2H5, and L is a leaving group as defined herein. The present invention also comprises bleaching and detergent compositions containing compounds of the general .~

.. ..~
, i~2343~

formula descr1bed above and a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution ~herein the ratio of peroxygen bleaching compound to peroxygen bleach activator compound is about 10:1 to about 1:4.
This invention also comprises a method of making the alpha-substituted alkyl or alkenyl compounds above, where L is an oxybenzene sulfonate9 comprising reacting the corresponding substituted acid chloride with the disodium salt of L under anhydrous conditions.
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to novel alpha substituted alkyl or alkenyl esters useful as peroxygen bleach activators. These activators, when used in combination with a peroxygen bleach compound capable of yielding hydrogen peroxide in an aqueous solution, at specific molar ratios of available hydrogen peroxide in solution to activator, provide extremely effective and efficient bleaching of stains from textilest Such compositions remove stains and/or soils from textiles, as well as the visible evidence of stains and/or soils. The bleaching activity of these compositions makes them particularly effective in the removal of dingy soils. Dingy soils are frequently a blend o~ particulate and greasy materials that build up on textiles after numerous washings; these soils give white textiles a gray tint. Removing soils of this type is sometimes referred to in the art as "dingy fabric clean-up".
The bleaching compositions employing the activators of the present invention provide this effective bleaching over a wide range of temperatures. Without the bleach activator compounds of`
the present invention, such peroxygen bleaching compounds would be ineffective and/or impractical at temperatures below about 60C.
The improved bleaching activity obtained by employing the activators of the present invention is observed when the bleach solution temperature is at least about 5C.
Compounds similar to those of the present invention which are known in the art can be logically separated into two classes. The :;

39~326 f~rst class of known compounds are the correspond1l19 un~ubst1tuted c~npDunds, c~npounds ~1th s1m~1~r or t~ent~tal ch~ln t~ngths ~nd leavlng groups but ~1thout the ehlor1ne, ~thoxy or ~thoxy gnoup subst~tuted ~t the alpha (2) posqt~on. The seeond cl~ss of kno~
S c~mpounds are cQnpounds ~th the chlor1ne, ~ethoxy or ethoxy subst1t~ltlon but possess~ng a ch~ln length (the ~lkyl or 21k~nyl ch~1n ~th the substltut~on~ o~ only 2-3 c~rbon ~toms. ~he ~ct~ators ~st s~mllar to those of the 1nstant învent~on ~
b~th of l;hese classes of conpounds suffer ~r~m the s~ne d~sadvan-1~ tage: they y~eld compounds (the a~t~ve component or spec1es) ~hich possess ~n offens~ve, unpleas~nt odor under ~ctual us~ge cond~t~ons (pH, temperature, etc.). Thls character~st~c ~alodor Er~kes the use of e~ther class of -known eompounds undes~r~ble fsr two reasons. First~ th~s odor ~s detecS~ble ~hen the compounds ~re pl~ced ~n solution, ~.e. dur~ng use. Second~ the ~lodor assoc~ated w~th these compounds lingers~ n~ng on llny text~le or ~abric which has been placed ~n a ble~Gll~ng sGlutlon cont~ning the~. Thus, tlhe ~nalodor ~s noticeable both ~ur~ny and ~fter use.
~he compounds of the present ~nvent~on, p~rt~cularl~ the 2~ ~lphl~ chloro s~lbst~tuted co~pounts, possess two s1gnlficant edvantages over the art-d1sclosed compounds ~scussed above. Most ~snpDrtangly, they do not gener~te9 either dur~ng or after use, the ~lndor ~h~ch ls character~st~c of the use of the ~rt~d~solosed co~ounds. Secondly, under conmon usage cond~t10ns, the co7npoun~s of the present ~nvent~on are frequently cllp~ble of prov~ding equi-v~lent peroxysen bleaching ~hile employing lower levels of per-- oxygen bleaching compound than would be required for the art-d~sclosed c~mpounds. In this context ehey are mnre efficient.
Peroxygen Bleaoh Act~vators - 30 The present ~nvent~on omprlses peroxygen bleach activa~or conpounds of the general fonrul~

R - ~ L (1~

~ 35 ~here~n R ~s a branched or l~near ~lkyl or alkenyl ~roup haY~ng ,, ,~,.

~23~326 from about 4 to about 14 carbon atoms; Rl is H, CH3, C2H~ or C3H7;
X' ~s Cl, OCH3 or OC2H5; and L is a lea~ing group the coniugate acid of which has a PKa in the range of from ~bout 4 to about 30, or a sugar. These compounds, when used in combination with a peroxygen bleach~ng compound capable Gf yielding hydrogen peroxide in an aqueous solu~ion, provide particularly effect~ve peroxygen bleaching over a wide range of temperatures and conditionss L in the above formula can be essentially any useful leav~ng group. A leaving group is any group that ~s d~splaced ~rom the bleach activator in a peroxygen bleaching solution as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This perhydrolysis reaction results in the formation of a percarboxylic acid. 6enerally, for any group to be useful as a leaving group in the compounds and eompositinns of the present invention, it must exert an electron attraction or an "electron attracting effect". This facilitates the formation of the peroxy acid anion. Leaving groups that exhibit this behavior are those with a corresponding conjugate acid that has a Ka in the range of from about 4 to about 30, preferably about 4 to 16, more preferably about 6 to about 13, and even more pre-~erably from about 7 to about 11. If sustained bleaching activity over a long period of time is desired, then employing groups with PKa values other than those ind1cated as preferred (different perhydrolysis rates), or mixtures of groups having various PKa values, may be desirable.
Preferred bleach activator compounds of the present invention are those of the above general formula (I) wherein R, Rl and X' are as defined in the general formula (I) and L is selected from the group consisting of:
'~

~Z3~L3Z6 0~, - O ~ R, n g~ f H2 G~
-O~C~R, -N~ ~IH
C
o ~,~2 -~-eH ~ c - CH ~ CH2, p~2 2 R or 0~ CHR Y
~0-C ~ CHR, ~here~n R2 ls ~n alkyl cha~n conta~nlng ~ bout 1 to about 8 15 c~rbon atoms, R ~s H or ~n ~lkyl thain cont~n~ng from ~bout 1 1:o ~Ibout 8 carbon ~toms, ~nd Y 1s H or ~ group wh~ch proYides solubllity t~s def~ned here1n) to the bleach actlv~tor ~wpounds of the present ~nvent10n ~n water at 5C or ~5C, herein~fter referred to as ~a solub~llz1ng group~O ~he preferred solub11~zing 20 groups are -S03M, -C00 M, -SojM, ~-N R34)X; ~nd O~NR24"1nd ~ost prefersbly -S03M md -COO M, ~dhere~n R ls an ~lkyl ~th~ln . contaln~ng from about 1 to ~bout 4 ~ar~on aton#g M ~s ~ c~t~on - ~hlch, ~hen co~ ned ~3~th X, provides solubil~ty to the bïeach ~clt~tor c~pounds of the present ~nventlon. ~refer~bl~y, M ls ~n 25 ~lkal~ ~etal, aDn~um or subst~tuted ~mnon~um caS~on, ~th sod~m ~nd pot~ssium being most preferred"3r~ X ~s a hal1de, hydrox~de9 methylsulfate or acetate ~n~on. It shvuld be noted th3t ble~ch activ~tor compounds of the present lnvent~on ~Irhich possess ~
`~ leav~ng ~roup th~t does not conta~n a solub~ ng group should be ~0 ~ell dispersed khen employed ln ~ ble~ch~ng solut~on ~n order to ~ss~st ~n the~r dissoluSlon. By pro~ding solub~l~ty, is used here~n, ~s ~e~nt th~t the group or groups selected ~ke the f~nal ~le~ch ~ct~ tor compound suff~c~en~ly soluble to prov~de a concentr~t~on at least 3 parts per ~lllon of ac~1v~tor ~n the 35 blleaeh solutîon ~t elther 5~C or 45~C, or at bo~h ~emperatures.

~3~3Zt;

~ lph~ substltuted (Cl~ or OCH3 or 0C2H5~ ~lkyl or ~lkenyl earboxyl 1c ae1d d1019 poly~l, and sug~r es~ers ~re also useful .
~referred sugar ester ble~ h act~Yator c~pound~ of the present ~nvent~on 1ntlude glucose, sucrose, ~nd lactosg esters of the fonmula ~H20A

AO ~ A A

~ ~H;~OA

~320A C~2A

.~o ~hereln A is H or R ~

whereln R ~s D branched or l~near ~lkyl or ~lkenyl group having from about 4 to about 14 carbon atoms; Rl ls H, CH3, C2H5 or C3H7;
ond X' ls Cl, OCH3 or OC2H5; prov~ded that ~t least one A is not ~ 30 H. tn preferred sugar ester peroxygen bleach activator eompounds ; of the presenS inventlon, no A 1s H~ .
Preferred bleach sctlv~tor oompounds of the p~esent lnven~ion are ~lso those of the above gener~l fon~ula (I) ~here~n L, X' and Rl ~re as deflned 1n the general fonmula ~ nd ~ ~s ~ br~nched 35 or l ~near,, and preferably 1 1neir~ yl group conta~n~ng from ~bouS 4 to ~bout 10 c~rbon atoms. Yhose havlng a l~near alkyl R

. ,~

3~3;~6 gro~Jp c~nta~nlln~ from ~bout 6 to ~bout 10 are ~ore preferred.
~ven ~ore preferred ~re bleach ~ctlvator c~npounds of the presen~
~nvent10n af the ~bove 9eneral fs~ula (1) ~erglln ~ ~3 i~S deflned 1n-the gener~l fonnul~ and R ~s a linear ~lkyl ch~ln conta~ning 5 fr~n obou1; 6 to ~bout 8 c~rbon ~tons.
Preferred ble~ch ~ctlvator canpounds of the present 1nvent~on ~re those of the ibove gener~l fo~ul~ where~n R and L ~r@ ~S
defined above, and Rl ls H or C2H5, w~th R~ ~s H part1cularly preferred.
7hus, the præferred bleach act~votor conpounds of the present ~nvent10n are those of the above general forn~la (1) whereln R ~s a l~near ~lkyl cha~n conta~n1ng fmm ab~ut 6 ll:o albout 10, and Inore prefer~bly from about 6 to about 8 carbon ~toms" Rl is H or C2H5, ~nd prefer~bly H, X' ~s Cl, and L ~s selected from the group lS conslst1ng of:

o ~) ~ 2 N'~H2 ~
-0-C-R, - ~ ~NH
C

'd -0-CH ~ C - CH ~ CH2, -~-C ~ EHR3, whereln P~, R29 R3 and Y are as def~ned ~bove.
More preferably, the ble~ch activator compounds of the present ~nvent~on ~re those of the ~bove gener~l ~ornula (I~
~hereln R ~s a 11near ~lkyl group conta~n~ng ~ron; aboul: 6 ~o about 10 carbon ~toms, ~' ~s Cl, Rl ls H or C2H5~, preferably H" and L ~s selected from the ~roup eons~stln~ of:

~3~326 ~2 p~2y ~~5 ~ {~Y and -0~>
~herelin R2 1s as deflned above nd Y 1s -S03M or -C00 M ~hereln M 1 s ~s def 1 ned ~bove .
~referred branched ~lkyl cha~n ble~ch ~ctlv~tor compounds of ~he presen~ lnvent~on are those of the ~bove general fo~laula (I) ~here~n R ls ~ br~nched alkyl ch~1n conta~n~ny from ~bout 6 to about 12 tarbon stoms ~hereln the longest l~ne~r allkyl port10n of sa~d cha~n cont~ins from about 4 to ~bout 10 c~rbon atoms~ X' ls Cl, Rl ~s H or C2H~, ~nd L ~s selected fro~n the group conslstlny o~

-~. -0{~ and -0~
~Aereln R2 ls an all~yl ch~1n eonta~nlng from about 1 to about 8 c~rbon atoms, Y ~s -S03 M or -C~ M ~here~n ~1 ls sodium or potassium.
Highly preferred bleach activator compounds of the present ~nvent~on are those of the above general fonnula (I) ~here~n R ~s ~ linear alkyl chain conta~ning from about 6 to ~b~ut 10, ~nd prefer~bly fr~ about 6 to about 8 ~arbon ~toms9 R ls H or C2H~, ~nd preferably H, X ls Cl and L is selected from the group cons~st~ng of:
y ~2 ~2y ~0~, -O~Y and -0~>
~5 ~hereln R is as defin2d ~bove an~ Y ls -S03M or -C00 M~ ~here~n M ~s ~s defined ~bove.
The ~ost highly preferred bleach ~ct~vator compounds of the present invent~on Dre of the fonnula:

R - CH - ~ - ~S03M or ~3~
R _ ~H ~ ~-~? -where~n R ~s a l~ne~r ~ cha~n contll~n~n~ from about 6 to ~bout 1OD and prefer~bly from about 6 to a~out 8~ c~rbon atoms, aQd 19 1s sodiu- or potasslum.

.

.

123~3ZÇ~

Representative peroxygen bleach activator compound5 of the present ~nvention include, without l~ita~on, 6`
CH3-(CH2)s-~H-C-O ~ so3Na Sodium 4-( 2-rhl orooctanoyloxy)benzenesulfonate;

CH3-(cw2)6-~ c-o~so3Na 10Sodium 4~(2-chlorononanoyloxy)benzenesulfonate;

C~3-(cH2)7-c~-c-o ~ S03Na Sodium 4-(2-chlorodecanoyloxy)benzenesulfonate;
15CH3 f-cH2-clH~-cH-~-o ~ S03Na Sodium 4-(3,5,5-trimethyl-2-chlorohexanoyloxy)benzene sulfonate;
~H3_(CH2,3- 3 C - ~s03Na Sodium 4-(2-chloro-2-ethyl-hexanoyloxy)benzenesulfonate;
R

CH3-(CH2)5 fH C O ~
25 Cl ~3Na Sodiùm 2-(2-chlorooctanoyloxy)benzenesulfonate CH3-(CH2)6-CH-~- ~
~1 3Na 30~Sodiu~ 2-(2-chlorononanoyloxy)benzene sulfonate CH3 (CH2) Cl C02Na Sodium 2-(2-chlorooctanoyloxy)benzoate .. ~,. .......

3~;

CH3~ 2)~-~H-~-O;~) 2Ib Ssd~um 2-~2 chlorononanoyloxy)benzoate CH3- (~H2)5~~~~~~c02Na 5Odium 4-(2-chlorooctanoyloxy)benzoate and ~H3-(~H2)6~ 0~o2Na Sod~um 4-(2-chlorononanoyloxy)benzo~te ~he Peroxygen Bleach~ng Composlt~on The present ~nvent~on ~lso compr~ses ~le~ching and detergent lS compositions contain~ng compounds of the.gener~l fonmula ~I) descr~bed ~bove and a peroxygen bleach compound capable of yiel~ing hydrogen peroxide in ~n aqueous solut~on where~n the rat~o of peroxygen bleach compound to peroxygen bleach activ~tor cGmpound ~s ~bout 10:1 to about 1:4, by ~eight of the ecmpos~t~on.
R~t~os of ~bout 3:1 to ~bout 1:2 ~re præferred, ~ith r~t~os of ~bout 3:1 to about 1:1, by &eight of the s~mpos~t~on, part~cul~rly preferred.
~ he preferred rolar r~tio of av~lable hydrogen perox~de generated ln solution (the ble~chlng solut~on or l~quor) by the 25 pero~ygen bleach compound to bleach ~ctivator compound ~s ~bout 3:1 to a~out 1:3. It should be noted that such a r2tio an ~15 gener~lly be expressed ~s the molar rat~o of peroxyyen bleach compound to peroxygen bleach act~vator bec~use the vast major~ty of peroxygen bleach oompounds theoretlcally y~eld one ~le Gf 30 hydrogen peroxide (ln solutlon) per msle of peroxygen bleach compound.
It w~ll be apprec~ted by exa~n1ng the preferred rat~os ~of peroxygen bleach compound to peroxygen bleach act1Yator compound~
descr~bed ~bove, that the bleach~ng cwposl~lons of t~e presen~
35 ~nvent~on possess 3 secor,d s~gnlf~cant ~dv~nt~ge oYer ~any Yery s~lnllar ~rt-d~sr~osed co~pounds; they ~re extren~ely e~f~c~ent.

~3 ~ 3~6 Much lower levels of the peroxygen bleach activator compounds of the present invention are requ~red (on a molar bas~s) to achieve bleaching performance equivalent to that 3f many very similar art-disclosed compounds.
The peroxygen bleach activators of the present lnvention are partkularly useful in peroxygen bleach~ng compositions designed for the surface bleaching of fabrics or textiles, especially dingy soil clean-up. The peroxygen bleaching compounds useful herein, i.e., in combination with one or more of th~ peroxygen bleach 10 ac~ivators of the present invention, are those capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide; the alkali metal peroxides; organic peroxide bleaching compounds such as urea peroxide; and inorganic persalt bleaching compounds, such as the 15 alkali metal perborates~ percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds, or mixtures of two or more activator compounds, can also be used, if desired.
Preferred peroxygen bleach activator compounds of the present 20invention for use in bleaching compositions include sodium 4-(2-ch7orooctanoyloxy)benzenesulfonate; sodium 4-(2-chlorononanoyl-oxy)benzenesulfonate; sodium 4-(2-chlorodecanoyloxy)benzene-sulfonate; sodium 4-(395,5-trimethyl-2-chlorohexanoyloxy)benzene-sulfonate; sodium 4-(2-chloro-2-ethylhexanoyloxy)benzenesulfonate;
25sodium 2-(2-chlorooctanoyloxy)benzenesulfonate; sodium 2-(2-chlorononanoyloxy)benzenesulfonate; and sodium 2-( ~chlorodecan-oyloxy)benzenesulfonate; sodium 4-(2-chlorononanoyloxy)benzene-sulfonate; sodium 4-(2-chlorodecanoyloxy)benzenesulfonate; and sodium 4-(2-chlorodecanoyloxy)benzenesulfonate.
Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. More preferably, the peroxygen bleaching compound is selec~ed from the 35group ~onsisting of sod~um perborate monohydrate, sod~um perb3rate tetrahydrate, and sodium carbonate peroxyhydrate, Particularly ~ '" _1.'' 3~3 preferred are sodiu~ perborate tetrahydrate and sodiu~ perborate monohydrate. Sod~um perborate monohydrate is espec~ally preferred because i~ is stable during storage yet dissolves very quickly in t~e bleaching sclu~ion. It is believed that such rapid dissolu-tion results in the formation of higher levels of percarboxylicacid and, thus, enhances surface bleaching perforTance.
Useful le~els of peroxygen bleach compound within the bleach-ing compositions of the invention are from about 0.1~ to about 95%, and preferably from about 1X to about 60~, by weight of the bleaching composition, preferably utilizing the ratios described abo~e. When the bleaching compositions within the invention are also detergent compositions it is pre~erred that the level of peroxygen bleach is from about 1~ to about 20~, by weight of the detergent composition, preferably utilizing the peroxygen bleach compound:peroxygen bleach activator weight ratios described abo~e.
The level of bleach activator compound within the composi-tions of the in~ention is from a~out 0.1~ to about 60%, and preferably ~ro~ about 0.5~ to about 40~, more preferably about 0.5~ to about 20~, by weight of the bleaching composition, pre-ferably utilizing the peroxygen bleach compound:p~roxygen bleachactivatcr weight ratios described above. When the bleaching compositions within the invention are also detergent compositions it is preferred that the leYel of bleach actiYator is from about 0.5X to abou~ 20%, and more preferably about 5~ to about 20X by weight of the detergent composi~ion, preferably util king the peroxygen bleach compound:peroxygen bleach acti~ator weight ratios described above.
ln a particularly preferred embodiment of the present invention the bleach activator compounds are employed in a mixture ~0 with other conventional peroxygen bleach activators. For example, mixtures of the compounds of the present invention a~d the peroxygen bleach activators described in U.S. Pa~ent 3,1309165 (~rocklehurst) issued April 21, 1964; ~ritish Paten~ Specification 864"798, published April 6, 1961; British Patent Specification 836,988D p~blished June 9, 1960; U.S. Patcnt 4,2~3,301 (Biehl) issued August 11, 1981; U.S. Pa~ent 3,0757921 (Brocklehurst et al) 3~3f~

issued January 29, 1963; U.S. Patent 4,412,934 (Chung et al) issued November 1, 1983; and U.S. Patent 3,936,537 (Baskerville et al) issued February 3, 1976, may be em-ployed. Preferred peroxygen bleach activators for use in combination with the compounds of the present invention in the bleaching compositions of the present invention include sodium 4-octanoyloxybenzene sulfonate, sodium 4-nonanoyloxybenzenesulfonate, sodium 4-decanoyloxybenzene sulfonate, tetra acetyl ethylene diamine, tetra acetyl methylene diamine; and tetra acetyl glycouril. Especial-ly preferred peroxygen bleach activators are sodium 4-nonanoyloxybenzenesulfonate, sodium 4-octanoyloxybenzene-sulfonate and sodium 4-decanoyloxybenzene sulfonate. The ratio of conventional activators to the activator of the present invention is from 1:9 to 9:1, preferably from 3:7 to 7:3, more preferably from 2:3 to 3:2. A highly desir-able mixture comprises the substituted activators of this invention and the corresponding unsubstituted activators.
Such a mixture can result from using a mi~ture of acyl groups resulting from the method of manufacture. Especi-ally preferred combinations are those in which the acyl groups have carbon chain lengths from about C8 to about The mixtures described above deliver several unexpected benefits. The combination of substituted activators and unsubstituted activators exhibits a preferred odor profile under the soil conditions of the typical wash load as com-pared to the individual activators. The combination of the alpha-chloro substituted activators and the linear unsub-stituted activator exhibit very good odors under typicalsoil loading conditions. Further, mixtures show no signi-ficant loss in bleaching effectiveness from the 100% linear unsubstituted activator as shown herein. Further, mixtures allow a decrease in the amount of perborate in a detergent composition without a resulting decrease in bleaching effectiveness. Finally, the combinations offer improved solubility, improved low temperature bleaching, and a :
.. . . .

~Z34326 C05t savings benefit. By using the mixtures9 a l~wer purity of the alphachlorinated activator is acceptable and even desirable.
This greatly reduces the oost in~olved in ~aking the activator compounds herein.
The bleaching compositions of the present invention, in-cluding detergent compositions, are preferably employed at a pH
(i.e., bleaching or detergent solution or liquor) of about 8 to ~bout ll, with a pH of about 8.5 to about 10.5 preferred.

The character of peroxygen bleach activator compGunds can be significantly altered during storage. (See U.S. Patent 4,4l2,934, Chung, et. al., issued November 1, 1983.) This is particularly true of the bleach actiYator compounds of the present invention.
If s~ored as part of a bleaching or detergent composition, the peroxygen bleach activators of the present invention may interact with other bleaching (e.g., perborate) or detergent components.
They may al50 react with the moisture inherently present in e~ther type of composition, or with the moisture in the environment in which they are stored. The bleach activator compounds of the present invention must therefore be protected from the environment during stor~ge to retain efficacy. However, i~ is critical that the selected method of protecting the bleach activator compounds of the present invention from their environment (especially moisture~ during storage not substantially inhibit their ability to disperse in water.
~ his invention relates to a body containing stabilized, particulate peroxygen bleach activators which comprises specific bleach activators and binder or enrobing materials, both of which are defined herein. The peroxygen bleach activators incorpora~ed in the body have excellent storage stability (are well protected from their environment) and yet readily disperse and release in water. Also9 when the bodies are fonmed in the pract1ce of the present invention, a superior level of bleaching performance on textiles is obtained.

343~6 lt is preferred that the peroxygen bleach activator and binder or enrobing material are substantiatly evenly distributed throughout the body. The body must also have the proper density Compacting the bleach activa~or compound particles to form a body with a density within the invention and then coating it ~ith the binder material may not provide the maximum level of storage stability. Only when the bleach activator and binder mater;al are substantially evenly distributed throughout the body is the storage stability maximized. However, it is also essential that 13 the density of the body be above about 1.06 grams/cubic centimeter (g/cc), preferably above about 1.08 g/cc, most preferably from about 1.10 9/CG to about 1.30 g/cc. When the peroxygen bleach activator and binder or enrobing material are substantially evenly distributed throughout the body, densities below about 1.06 g/cc may not provide the desired level of storage stability.
Specific densities may be mRasured by a mercury displacement method, described as follows. Air is removed from a vessel containing a weighed sample of the particles (bodies), mercury is introduced, and the pressure increased in increments. The ra~e of volume decrease ~or density increase) is typi~ally one value when interparticulate spaces are being filled, which occurs first, and a different value when the Yoids in the particle are being filled.
The inflection point on the volume-pressure curve is taken as indicating the specific density of the particles.
2S To achieve maximum storage stability, th~ body should also be essentially free of moisture. The presence of excess free moisture will result in very poor storage stability because of the peroxygen bleach actiYator's susceptability to hydrolysis. Thus, preferred bodies contain less than about 5~ water, more preferably ~0 less than 3% water, and most preferably less than about 1.5X
wa~er, by weight of the body .
Control of the particle size of the body is also of some importance for obtaining optimum storage stability and dispersi~ility in the wash water. It is preferred that the bodies of the present invention, when employed in a bleaching or detergent composition~ have a par~icle size distribution of from ~23~Z6 a~out 50 microns to about 2.5 millimeters wherein no more than about 5X of the bodies are greater than about 2 ~ eters. ~ore preferably, the bodies of ~he present inYention, when employed in a bleaching or detergent composition, have a particle size distri-bution of from about 300 microns to about 1.5 mill~meters.
The body can be made by essentially any apparatus that i5suitable to substantially evenly distribute the bleach activator and binder ~aterial throughout the body and compact the body in order to obtain the required density. For example, powder blenders can be utilized to mix the bleach acti~ator and binder materi~l and then the mixture can be passed through a radial or axial extruder. A compaction press may also be employed to form the body. Radial or axial extruders are preferred because it is believed tha~ they produce a body in which the bleach acti~ator has both superior storage stability and dispersibility in the wash water. When the bleach activator and binder material are mixed, the binder material is preferably in fluid form. This can be accomplished by heating the mixture until the binder material mRlts. When employing binder materials tha~ decompose rather than melt upon heating, an aqueous solution can be formed.
The following is a detailed description of the essential components of the body containing the peroxygen bleach ac~ivators of the present invention. All percentages, parts and ratios are by ~eight of the body unless otherwise indicated.
~he leYel of bleach activator useful within the bodies of the present invention is from about 50X to about 99.5%, preferably about 50% to about 98%, and more pre~erably from abou~ 85% ~o about 96~, by weight of the body.
Bleaching compositions employing the bodies of the present ~ invention comprise from about O.lX to abou~ 60X, and preferably ; about 0.5% to about 40~, by weight of the composition of the bndies of the present inven~ion, and from about O.lX ~o about 95~, preferably about 1~ ko about 60~, by weight of the composition, of a peroxygen bleaching compound capable of yielding hydrogen peroxide in an aqueous solution. ~hen these bleaching compositions are also detergent composi~ions, i~ is preferred that ~L23~a3~2 ~he level of bleach bodies is from ~bout 0.5~ to ~bout 20~, by weight of the detergent composition, ~nd that the level of peroxygen bleaching eompound is from about 1~ to about 20%, by weight of the detergent composition, and th~t the composition ~urther comprises about 1X to about 30~ of 2 detergent surfactant.
Preferred ratios of bodies:peroxygen bleaching compound are the same as those described herein for activator alo~ie to peroxygen bleaching compound.
It is also preferred that the bleach activator particle size 10 distribution within the bleaching or detergent eomposition is from about 5 microns to about 2.5 millimeters. More preferably, no more than about 2~ of the particles are greater than about 2 millimeters. ~ost preferably, the particle s~ze d~stribution is from about 25 microns to about 150 microns.
~he Binder or Enrobing Materials The materials that can be util ked ~s binders or enrobing materials are the nonionic surfactantsl polyethylene glycols, f~tty acids, anionic surfactants, ~ilm forming polymers and mixtures of these materials. lt is believ~d that such binder or enrobing materials are not reactive with the blea6h activators of the present invention. lf the body is placed in a detergent composition, the binder or enrobing material should not be reactive with the components of the detergent composition upon stora~e. ldeal binder or enrobing ~aterials ha~e a low ~ygroscopicity upon storage but should be soluble or dispersable 1n water. This allows for dispersion and release of the peroxygen bleach 3cti~ator in the bleach or wash solution. It is also essentiat that the employed binder or en-Dbing materials do not melt below about 40C. ~he binder would likely melt upon storage;
~0 frequently ~he storage temperature for such compositions is as h1gh as 40C. Any melting of the binder or enrobing material results in the bleach activator being quite unstable. ~While some of the binder materials within the inventi~n will decompose rather than melt upon exposure to of heat, the te~perature at which such binder materials decompose is well beyond any temperature a~ which the bodie~ w~ll likely be stored.) 23~3Z6 Examples of other nonionic surfactants that can be utilized as binder or enrobing materials are the conden-sation products of primary or secondary aliphatic alcohols having from 8 to 24, and preferably about 9 to about 18, carbon atoms, in either a straight or branched chain con-figuration, with from about 35 to about 100 moles, and preferably about 40 to about 80 moles, of ethylene oxide per mole of alcoholO The preferred nonionic surfactants are prepared from primary alcohols which possess either linear (such as those derived from natural fats, or pre-pared by the Ziegler process from ethylene, e.g., myristyl, cetyl, and stearyl alcohols), or partly branched carbon chains (such as the Dobanols and Neodols which have about 25% 2-methyl branching, Dobanol and Neodol being Trade Marks of Shell; Synperonics, which are understood to have about 50% 2-methyl branching, Synperonic being a Trade Mark of I.C.I.; or the primary alcohols having more than 50~ branched chain structure sold under the Trade Name Lial, by Liquichimica)~
Other suitable nonionic surfactants are the poly-ethylene oxide condensates of alkyl phenols. These in-clude the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms, in either a straight or branched chain configuration, with ethylene oxide. The ethylene oxide is preferably present in amounts equal to about 35 to about 100, more prefer-ably about 40 to about 80, moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived, for example, from polymerized propylene, di-isobutylene, octene and nonene.
Nonionic surfactants suitable for use herein also include the compounds formed by condensing ethylene oxide with a hydrophobic base. The hydrophobic base is formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic nonionic detergents are items of commerce. They are available from Wyandotte Chemicals Corporation as Pluronics~.

~.~3~3Z~

Suitable polyethylene glycols are homopolymers of ethylene oxide having the general formula H(C2 4 )~ ' have an average molecular weight of from about 2,000 to about 15~00G, preferably from about 3,000 to about 10,000 and most preferably from about 4,000 to about ~,000.
The fatty acids suitable for use in the bodies of the present invention include the higher fatty acids con-taining from about 8 to about 24, and preferably from about 12 to about 18, carbon atoms. It has also been ob-served that mixtures of fatty acids and nonionic binder materials, e.g., polyethylene glycols or nonionic surfac-tants, provide the bleach activator with particularly good storage stability and dispersibility in the wash water.
It is believed that fatty acids reduce the hygroscopicity of the nonionic binder materials and that the nonionic binder materials improve the dispersibility o~ the fatty acids. p~ of the body can also be controlled with such materials when this is important.
Suitable anionic surfactants useful as binder or enrobing materials in the bodies of the present invention include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sul-furic reaction products having in their molecular struc-ture an alkyl group containing from about 8 to about 20 carbon atoms and a sulfonic or sulfuric acid ester group.
~Include in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms), and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms in a straight or branched chain configuration. These are described in U.S. Patents 2,220,099 and 2,477,3~3. The preferred anionic surfac-tants are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Cll 13LAS.

3 ~ 3 2 6 Other anionic surfactants useful as binder or enrobing ~aterials in the bodies of the present invention are the water-soluble salts of the hi~her fatty ~c~ds or Usoaps". This includes alkali metal soaps such as the sodium, potassium, ammon-5 - ium, and alkylolammonium salts of the higher fatty acids oontaining from about 8 to about 24, and preferably from about 12 to about 18~ carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
Anionic surfactan~s useful as binder or enrobing materials in the bodies of the present invention also include the the sodium alkyl glyoeryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule or unit and wherein the alkyt groups contain from about 8 to about 12 sarbon atoms; and the sodium or potassium salts of alkyl ethylene oxide ether sulfates ontaining about l to about 10 units of ethylene oxide per molecule or unit and wherein the alkyl group contains from about ~0 to about 20 carbon atoms.
Still other anionic surfactants useful as binder or enrobing mdterials in the bodies of the present inYention include the water-soluble salts of thP esters of alpha-sulfonated fatty acids containing from about S to about 20 carbon atoms in the fa~ty acid group and from about 1 to about 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to about 9 carbon atoms in the aoyl group ~ and from about 9 to about 23 carbon atoms in the alkane moiety;
the water-soluble salts of olefin and paraffin sulfonates containing from about 12 to about 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from abou~ 1 to about 3 carbon atoms in ~he alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
Suitable film ~onning polymers useful as binder or enrobing m~terials in the bodies of the present invention are the polymers 3~6 - ~7 -derived from the monomers such as vinyl chloride, vinyl alcohol, furan, acrylonitrile, vinyl acetate, methyl ac-rylate, methyl methacrylate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide~ ethy-lene, propylene and 3-butenoic acid.
Preferred polymers of the above group are the homo-polymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the co-polymers contain at least about 50%, and preferably at least about 80%, by weight, units derived from the acid.
The particularly preferred polymer is sodium polyacry-late. Other specific preferred polymers are the homo-polymers and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene and vinyl methyl ether~ These polymers are commercially available under the trade names Versicol and Gantrez.
Other film-forming polymers useful as binder or en-robing materials in the bodies of the present invention include the cellulose sulfate esters such as cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellu-lose sulfate, methylcellulose sulfate and hydroxypropyl-cellulose sulfate.
Surprisingly, very small levels of binder or enrobing material within the body are required. The level of bin-der material useful within the bodies within the inventionis from about 0.5% to about 50%, preferably from about 2%
to about 50%, and more preferably from about 4% to about 15% by weight of the body.
Examples of preferred binder or enrobing materials in-clude the fatty acid esters of alcohols, diols and polyols.For example, sorbitan fatty acid esters selected from the group sorbitan monolaurate, dilaurate, trilaurate, monopal-mitate, monostearate, distearate, tristearate, monooleate, dioleate, and trioleate, are preferred. These materials are items of commerce and are known as "Spans", a Trade Mark of the I.C.I. Amercias, Inc. Ethoxylated varieties of these compounds are also useful. For example, sorbi-tan esters having an average total level of ethoxylation of from about 4 to about 100, and preferably about 20 to ~i~
t, ~23'~3~

about 85 moles of ethylene oxide per mole of sorbitan, are preferred.
Particularly preferred binder materials include sor-bitan monopalmitate, sorbitan monostearate, sorbitan di-stearate, and sorbitan tristearate. Polyethylene glycolshaving an average molecular weight of from about 4,000 to about 8,000 are also useful and preferred. A mixture of lauric acid:PEG 8000, in a weight:weight ratio of about 2:1 to about 1:2, more preferably about 1:1, is also preferred.
The binder or enrobing material need not be completely inert; the binder or enrobing material can be selected to benefit the overall bleaching activity of the system. For example, employing 14~, by weight of a body, of C13LAS as the binder for the peroxygen bleach activator 4-(2-chloro-decanoyloxo)benæenesulfonate can significantly increase the rate of solubility of the peroxygen bleach activator.
The bodies of the present invention may also contain all of the usual components of detergent compositions in-cluding the ingredients set forth in U.S. Patent 3,963,537, Baskerville et al., so long as they are inert with respect to the bleach activator and binder material. Such com-ponents include other peroxygen bleach activators, color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, ger-micides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
In a highly preferred embodiment, the bodies of the present invention comprise (a) from about 85% to about 96% of a pe~oxygen bleach activator compound having the general formula R - C - C - L
~1 wherein R is a straight or branched chain alkyl or alkenyl having from about 4 to about 14 carbon atoms;
R is H or C2H5, X' is Cl, and L is selected from the group consisting of O ~ SO3M

.

3~t;

and ~ C02 M whereln M is sod~um cr potass~um; and (b) about 4% to about 15X of a binder material selected fr~m the group conslsting of sorbitan fatty acid esters, ethoxylated varieties of these sorbitan esters hav1ng an aver~ge total level of . ethoxylation of from about 4 to about 8 moles of ethylene ox~de per mole of sorbitan; linear alkylbenzenesulfonates ln which the average number of carbon atoms in the alkene moiety is about 11 to about 13; aliphatic alcohols containing between 9 and 18 carbon atoms ethoxylated with between 40 and 80 moles of ethylene oxide;
sodium polyacrylate; polyethylene glycols having a molecular weight of from about 4000 ~o about 8000, fatty acids containing from about 12 to about 18 carbon atoms; and mixtures thereof; the density of said body is from about 1.10 g/cc to about 1.30 g/cc, said body contains less than abou~ 1.5% water and said body has an average particl~ size distribution of from about 300 microns to about 1.5 ~illimeters.
REACTION METHOD
In accordance with the reaction method of the present inven-tion~ the alpha-substituted alkylphenylsulfonates are prepared by contacting the corresponding alpha-substituted ac~d chloride with disodiu~ phenolsulfonate under anhydrous conditions. A represen-tation of this reaction is as follows:

R - C - ~ - Cl + Na O
~5 X

R - C - C --0~503Na wherein R is a straight or branched chain alkyl or alkenyl having from about 2 to about 20 carbon atoms~ X is H, Cl, OCH3 or OC2H~, and R1 is H or C2H5. Preferred ac~d chlorides for use in the ~ethods of the present invent~on are those of the above general reaction formula wherein R is about 4 to about 12 carbon atoms, and more preferably about 6 to about 8 carbon atoms. Accordingly.
the present process is particularly useful ~or prepar~ng sodium ~l;2~3~3;~6

4-(2-chlorooctanoyloxy)benæenesulfonate; sodium 4~(2-chlorononanoyloxy)benzenesulfonate; sodium 4-(2-chlorode-canoyloxy)ben~enesulfonate; sodium 4-(3,5,5-trimethyl--2-chlorohexanoyloxy)benzenesulfonate; sodium 4-t2-chloro-2-ethylhexanoyloxy)benzenesulfonate; sodium 2-(2-chloro-octanoyloxy)benzenesulfonate; sodium 2-(2-chlorononanoyl-oxy)benzenesulfonate; and sodium 2-(2-chlorodecanoyloxy)-benzenesulfonate.
Both of the starting components necessary for the method of the present invention can be prepared by conven-tional means. The acid chloride starting component may be prepared by conventional methods, or by the regiospecific methods described in U S. Patent 4,148,811, Crawford, is-sued April 10, 1979; or U.S. Patent 4,368,140, Crawford, issued January 11, 1983. The alpha-substituted carboxylic acid may also be prepared employlng the carboxylic acid, chlorine, a second strong acid, a free radical inhibitor and an organic acid anhydride as described in Example VI
of the present specification. The alpha-substituted car-boxylic acid can then be converted by conventional means,such as reacting the carboxylic acid with SOC12, PC13 or PC15, and the like, to obtain the acid chloride. The second starting component, the disodium phenylsulfonate, can also be prepared by conventional means. As repre-sented in Example IV, the monosodium salt can be put intosolution, an equivalent molar quantity of sodium hydroxide is added, and the water removed.
The present process is not limited with regard to the method of preparing either of the starting components.
The method employed to prepare either the acid chloride or the disodium phenolsulfonate plays no part in the practice of the present invention. For example, an unsubstituted acid chloride may be converted to an alpha-substituted acid chloride according to Example II, column 7, lines 5-11 of U.S. Patent 4,368,140, discussed above. The acid chloride so prepared can then be used as a starting component in the reaction of the present invention.
The process reaction herein can be carried out in the pre-sence or absence of inert solvents. For example~ monoglyme, , ,~
~ . , .

~3~ 3 d~glyme, toluene, and the l~ke, are good solvents for this reactlon. Other useful solvents include diox~ne, xylene, chloro-ben~ene, tetrahydrofuran ~nd t-butyl-methylether. Preferably, the reaction ~s carrled out with the use of monoglyme or diglyme.
These solvents are particularly useful due to their bo~l~ng point, with monoglyme most preferred. The react~on is carr~ed out under anhydrous conditions. 8y anhydrous conditions, as used here1n~ is meant that reaction environment or solvent ~s sufficiently free of water so that no side reactions take place. Preferably, any solvent employed contains less than about 5X, more preferably less than about 1X, and most preferably less than about 0.5~, water, by weight of solvent.
The reaction process of th~s ~nYention is exo~hermic.
Accord~ngly, the rate at which this reaction will proceed may be easily controlled by controlling the rate at which the heat is allowed to dissipate from the reaction environment. Because the heat from such a reaction is generally conducted away ~ia any solvent employed, selecting a solvent suoh as monoylyme with a boiling point of about 82-83C allows the reaction temperature to be controlled by solvent. Under such conditions, the reflux takes place at the bo~ling point of the solvent and the temperature is controll2d accordingly. In turn, the rate of the reaction is also controlled.
- While 1t is desirable to control the temperature of the reaction wi~h a solvent, it is not necessary to do so. The react~on method of the present invention may be conducted and maintained at any temperature which is high enough to allow the reaction to begin, but low enough to prevent decomposition of the desired product. Reactions of the present invention have reached temperatures of about ?77CC with no significant disad~antages becom~ns apparent. However, it is preferred that ~he reaction methods of the present invention be commenced and mainta~ned at about 15C to about 150C, more preferably about 15C to about 100C, and most preferably about 20C to about 100C.
Typically, the molar ratio of alpha-subst~tuted ac~d chlo-r~de:diso~ium phenolsulfonate will be about 4:1 ~o about 1:4, and 3~3~26 preferably about 2:1 to about 1:2. Most preferably, the molar ratio of alpha-substituted acid chloride:disodium phenolsulfonate is about 1:1.
Optional Components As a preferred embodiment, the bleaching compo-sitions of the invention can be formulated as laundry detexgent compositions. Thus, the bleaching compositions can contain typical detergent composition components and adjuvants. Such components include detergency surfactants and detergency builders. When used in such embodiments the bleaching compositions are particularly effective.
The bleaching compositions of this invention can therefore contain all of the usual components of detergent compositions. This includes, wichout limitation, the ingre-dients set forth in U.S. Patent 3,936,537, Baskerville, et al., issued February 3, 1976. Such components, in addition to detergent surfactants and builders, include other peroxy-gen bleach activators, color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, anti-oxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
Detergent Surfactants The amount of detergent surfactant included in the detergent compositions of the present invention can vary from about o% to about 75%, by weight of the composition, depending upon the detergent surfactant(s) used, the type of composition to be formulated (e.g. granular, liquid), the projected wash conditions and the effects desired. Prefer-ably, the detergent surfactant(s) comprises from about 10%to about 50~, by weight, more preferably from about 1% to about 30%, and most preferably from about 10% to about 25~, by weight, of the total composition. However, because of the reactivity of the peroxygen bleach activator compounds of the present invention, liquid detergent compositions containing water should be formulated to stabilize these compounds ,.
The detergent surfactants which can be in-cluded in the bleaching compositions of the present invention include any one or ..

~2~L3Z6 more surface active ~gents selected from anion~c, nonionic, z~itter~on~c, amphoterk and cat~onlc surfact~nts, and compatible mixtures thereof. Detergent surfactants use~ul herein include, without l~m~tat~on, those l~sted or described ~n U.S. Patent 3,664,96I, Norris, issued May 23, 1972, U.S. Patent 3/929,678, Laughlln, et al, lssued December 30, 1975, U.S. Patent 4,222,905, Cockrell~ 1ssued September 16, 1980, and ~n U.S. Patent 4,239,659, Murphy, ~ssued December 16, 1980. ~e follow~ng are repre-sentative examples of detergent surfactants useful in the present compositions.
Anion~c Surfactants Anlon~c surfactants suitable ln detergent compos~tions of the present invention are generally disclosed ~n U.S. Patent 3,929,678 to Laught~n et al., ~ssued December 30, 1975 at colunn 23, line 56 through column 29, l~ne 23. Classes of anionic surfactants include the following.
Water-soluble salts of the hlgher fatty acids, i.e., "soaps", are useful anionic surfactants in the present compositions. This ~ncludes alkal~ metal soaps such as the sodium, potassium, ammon-ium, and alkylolammonium salts of higher fatty ac~ds containingfrom about a to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct sapon-lfication o~ fats and oils or by the neutralization o~ ~ree fatty acids. Part~cularly useful are the sodium and potassium salts of the m~xtures of fatty acids derived from coconut oil and ~allow, .e., sod~um sr potassium tallow and coconu~ soap.
Useful anion~c surfactants also ~nclude the ~ater-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts; of organic sulfur k reaction products having in their ~0 molecular struc~ure an alkyl group containing from about I0 to ~bout 20 carbon a~oms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl por~ion of acyl groups.) Examples of this group of synthetic surfactants are the sod~um and potass1um alkyl sulfates, especially those obtained by sulfating the h~gher alcohots (alcohols h~ving from about 8 to about 18 carbon atoms) such as those produced by reduc~ng the ,~, .
~. .f'b 3 ~ 3 Z 6 - 34;
glycerides of tallow or coconut oil; the sod1um and potassium alkylben~ene sulfonates 1n which the alkyl group contains ~rom about 9 to about 15 carbon atoms, in straight cha~n or branched chain configuration, e.g., those of the type described in U.S.
Patents 2,220,099 and 2,477,383, are also useful. Especially useful are the linear straight chain alkylbenzene sulfonates in which the a~erage number of carbon atoms in the alkyl group is from about 11 to 13 carbon atoms, often abbreviated as Cl1 13LAS.
Other anionic surfactants useful in the bleach~ng composi-tions of the present invention are the sodium alkyl glyceryl ether sulfonates, especially those ethers (of h~gher akohols) ~eri~ed from tallow and coconut oil; the sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; the sodiuD or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about lO units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and the sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about l to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
Other anionic surfactants useful in ~he compositions of the present in~ention include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; the water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 car~on ~toms in the acyl group and from about 9 to about 23 carbon ato~s in ~he alkane moiety; the water-soluble salts of ole~in and paraffin sulfonates containing from about 12 to 20 carbon atoms; and the beta-alkyloxy ~0 alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Nonionic Surfactants Suitable nonionic surfactan~s for use in detergent composi-tions of the present invention are generally disclosed in U.S.Patent 3~929,678 to Laughlin et al., issued Deceæber 30, 1975 at ~23~Z~
- 3s column 13; 11ne 14 through column 16, line 6- Useful classes of nonionic surfactants useful in the composltions of the present invention include the following.
1. The polyethylene ox~de condensates of alkyl phenols. ~hese compounds ~nclude the condensat~on products of alkyl phenots having ~n alkyl group containing from about 6 to 12 carbon atoms ~n either ~ stra19ht shain or branched cha~n oonfiguration ~ith ethylene ox1de, the ethylene ox1de being present ~n an amount equal to 5 to 2S moles of ethylene oxide per mole of alkyl phenol.
The ~lkyl substituent ~n such compounds can be derived, for example, from polymæri~ed propylene, diisobutylene, and the like.
Examples of compounds of this type include nonyl phenol condensed w~th ~bout 9.5 moles of ethylene oxide per m~le of nonyl phenol;
dodecylphenol condensed with about 12 moles of ethylene ox~de per mole of phenot; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commer-~c~ally ava11able non~onlc surfactants of th~s type ~nclude Igepal C0-630, marketed by the GAF Corporation, and Triton X-45, X-114, X-100, and X-102, 311 aarketed by the Rohm & Haas C ~ any.
2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of e~hylene oxide. The alkyl chain of the aliphatic alcohol can either be stra~ght or branched, primary or secondary, and generally conta~ns from about 8 to about 22 carbon atoms. ~xamples of such ethoxylated alcohols include the condensat10n product of myr~styl atcohol condensed with about 10 moles of ethylene oxide per mole of alcohol; and ~he condensation product of about 9 moles of ethylene oxide witb coconut alcohol (a m~xture of fatty alcohols w~th alkyl chains Yarying in length from 1~ to 14 carbon atoms). Examples of commercially aYailable nonion1c surfactants of th1s type include ~ergito ~ 15-S-9, mar^
keted by Union Carb~de Corporation, Neodo ~ 45-9, Neodol 23-6.5, Neodol 45-7, and Neodol 45-4, marketed by Shell Chem~cal Company, and Kyro~EOB, marketed by The Procter ~ Gamble Company.
3. ~he condensation products of ethylene oxide with a hydrophob~c base formed by the condensation of propylene ox~de ~. , ~. , , 43Z~

w~th propylene glycol. ~he hydrophob~c port~on of these compounds has a molecular ~e1ght of from about 1500 to l800 and exhibits water ~nsolub~lity~ The addit~on of polyoxyethylene mo~eties to th~s hydrophob~c port~on tends to ~ncrease the water solubility of the molecule ~s a whole, and the l~qu~d character of the product is retained up to the point where the polyoxyethylene content i5 about 50X of the total weight of the condensa~ion product, which corresponds to cGndensation w~th up to about 40 moles of ethylene ox~de. Examples of compounds ~f this type ~nclude certain of the commerc~ally aYailable Pluronic surfactants, marketed by Wyandotte Che~ical Corporation.
4. The eondensation products of eth~lene oxide with the product resulting from the reaction of propylene ox~de and ethyl-ened~amine. The hydrophob~c moiety of these products consists Ot lS the react~on product of ethylenediamlne and excess propylene oxide~ the mo~ety ha~ng a molecular weight of from about 2500 to about 3000. Th~s hydrophob k moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40X to about 80X by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonion1c surfactant include certain of the commer-c~ally ava~lable Tetronic~compounds, marketed by Wyandotte Chemi-cal Corporation.

5. Semi-polar non~onic detergent surfactants wh~ch include waterDsoluble amine oxides containins one alkyl moiety of from about lO to 18 carbon atom~ and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides contain-ing one alkyl moiety of fr~m about 10 to 18 carbon atoms and 2 ~o mo~et~es selected from t~e group cons~st~ng of atkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and ~ater-soluble sulfox1des conta~ning one alkyl moiety.of from about 10 to 18 carbon atoms and a moiety selected from the group con-s~st~ng of alkyl and hydroxyalkyl moieties of from about 1 ~o 3 carbon atoms.

~;23~3Z6 - 37 ~
Preferred semi-polar nonion k detergent surfactants are the am~ne ox1de detergent surfactants haYing the formula R (OR )xNR 2 where~n R3 1s ~n alkyl, hydroxyalkyl, or alkyl phenyl group or m1xtures thereof containing from about ~ to about 22 carbon atoms;
R4 is ~n ~lkylene or hydroxyalkylene group conta1n~ng from 2 to 3 carbon atoms or mixtures thereof; x is from O to about 3; and each R5 ~s an alkyl or hydroxyalkyl group conta~n1ng from 1 to about 3 carbon atoms or ~ polyethylene ox1de group conta1n~ng from one to about 3 ethylene oxide groups. The R groups can be attached to e~ch other, e.g., through an oxygen or nitrogen atom to fonm a ring structure.
Preferred ~mine ox~de detergent surfactants are C10-C18 alkyl dimethyl am~ne oxide and C8-C12 alkoxy ethyl dihydroxy ethyl amine ox1de.

6. Alkylpolysacchar~des dtsclosed ~n U.S. Patent 4,565,647 Ramon A. Llenado, issued J~nuar~ 21, 1986, having a hydrophobic group containing from ~bout 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbo~ atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group con-ta~ning an Dvera~e of from about l~ to about 10, preferably from about 1~ to about 3D most preferably from about 1.6 to abou~ 2.7 s~ccharide units. Any reducing sacchar~de conta1ning 5 or b carbon atoms can be used, e.g. glucose, galactose and galactosyl m~iet~es can be substituted for the glucosyl moieties. (Optional-ly the hydrophobic group is attached at other positions, e.g. the 2-, 3~, 4-, positions e~c., ~hus giving 2 glucose or galactose as opposed to ~ glucoside or galactos~de.) ~ne intersaccharide bonds can be, for example ~etween the 1- position of the additional saccharid~ un~ts and the 2-, 3-, 4-, and/or 6- positions on the preced~ng sacohar~de units.
Optionally, and less desirably, there can be a polyalkylene-o~de ch~in ~oining the hydrophobic ~oiety and the polysaccharide molety. The preferred ~lkyleneoxide is ethylene oxide. ~ypical hydrophob~c groups ~nclude alkyl groups, either sat~rated or i23~326 unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, oarbon atoms.
Preferably, the alkyl group is a straight chain s~turated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or 5 the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, most preferably 0, alkyleneoxide moiettes. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetr2decyl~ pentadecyl, hexadecyl, heptadecyl~ and octadecyl, di-, tri-, tetra-, penta-, and hexa~lucosides, galacto-sides, lactosides, glucoses, fructosides, fructoses, and/orgalactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
~he preferred alkylpolyglycosides have the formula R20(CnH2nO~t(91YCsYl)~
wherein R2 is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, prefer-ably from about 12 to about 14, carbon atoms; n ~s 2 or 3, prefer-ably 2; t is from 0 to about 10, preferably 0; and x is from 1~ to about 10, preferably from about 1~ to about 3, most preferably from about 1.6 to about 2.7. ~he glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl-polyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside ~attachment at the l-position). The additional glycosyl units can then be attached between their l-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominately the 2 position.

7. Fatty acid amide detergent surfactants having the for-mula:
O
R6_C-NR72 wherein R is an alkyl group containing from about 7 to about 21 ~preferably from about 9 to about 17) carbon atoms and each R7 is selected from the group consisting of hydrogen, C1-04 alkyl, Cl-C~

;~

3~326 hydroxyalkyl, ~nd -(C2H40)~H where x varies from dbout 1 to about 3.
Preferred amides are C8-C20 ammoni~ amides, monoethanol-~m~des, diethanolamides, and ~sopropanol amides.
Ampholyt~c surfactants can be broadly descr~bed as deriYatives of al~phatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in ~hich the al1phatic moiety can be stra~ght chain or branched and wherein one of the aliphatic substituents c~ntains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group. See U.S. 3,929,678, Laughlin, et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of ampholyt~c surfactants.
2witterion~c Surfactants Zwitterion~c surfactants can be broadly described as deri-~at~ves of secondary and tert~ary amines, der~vatives of hetero-cyclic secondary and tert~ary amines, or derivatives of quaternary ammon~um, quaternary phosphonium or tertiary sulfonium compounds.
See U.S. Patent 3,929,6~8, Laughlin, et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.
....
Cationic Surfactants Cationic surfactants can also be included in detergent compos~tions of the present ~nvention. Suitable cationic surfac-tants ~nclude the quaternary a~monium surfactants havlng the formuta:
tR2(oR3) ][R4(oR3) ~ R5N~X-wherein R is an alkyl or alkyl ben~yl group having from about 8 ~0 to about 18 carbon atoms in the alkyl chain; each ~3 is selected from the group consisting of -C~CH2-, -CH2CH(CH3)-, -CH2CH(CH2-OH) , -CH2CH2CH2-, and m~xtures thereof; each R ts selected from the group consisting of Cl-C4 al~yl, Cl-C hydroxyalkyl, benzyl, ring structures formed by joining the two R~ groups, -CH2CHOHCHOH-COR6CHOHCH20H wherein R6 is any h~xose or hexose polymer having amolecular we~ght less than about ~000, and hydrogen when y is not :, ~Z3~3;26 0; R5 ~s the same as R4 or ls an alkyl shain where~n the total number of carbon atoms of R2 plus R5 is not more than ~bout 18;
each y ~s from Q to about 10 and the sum of the y values ls from 0 to about 15; and X is any compatible anion.
Preferred of the above are the alkyl quaternary ammonium surfactants, especially the mono-long chain alkyl surfactants described in the above fonmula when R5 1s selected from the same groups as R4. The most preferred quaternary ammon1um surfactants ~re ~he chloride, bromide and methylsulfate C8-C~6 alkyl tr1-methylam~onium salts, C~-C16 alkyl di(hydroxyethyl)methylammonium salts, the C8-C16 alkyl hydroxyethyldimethylammonium salts, and C8-C16 alkyloxypropyl trimethylammonium salts. Of the above~
decyl trimethylammonium methylsulfate, lauryl trimethylammonium chloride, myristyl trimethylammonlum methylsulfate and coconut trimethylammonium chloride and methylsulfate are particularly pre-ferred. The use of bromides is least preferred due to the possible formation of hypobromite.
Detergent Builders In addition to detergent surfactants, detergency builders can be employed in the bleaching compositions o~ the present invention. When included, the level of detergency builder of the bleaching compositions is from OX to about ~0%, preferably from about 10% to about ~OX, by weight, and most preferably from about 20% to about 60X, by weight of the composition. Water soluble inorganic or organic electrolytes are suitable builders. The bu1lder can also be water-1nsoluble calcium ion exchange ~aterials; nonlimiting examples of suitable wa~er-soluble, ~norganic detergent builders include: alkali metal carbon~tes, borates, phosphates, bicarbonates and silicates. Specific examples of such salts include sodium and potassium tetraborates, b1carbonates, carbonates, orthophosphates, pyrophosphates~
tripolyphosphates and metaphosphates.
Suitable detergent builders 1nclude crystalline aluminosili-cate 10n exchange materials ha~ing the formula:
Naz~(AlO2)z ~SiO2)y] XH2 -: LZ343ZG

wherein z and y are at least about 6~ the mole ratio of z to y ls from about 1.0 to about 0.5; and x is from about 10 to about 264, Amorphous hydrated aluminosllicate ma~erials useful herein have the empirical formula Mz(zAlo2 ysio2) wherein M is sodium, potassium, am~onium or substituted ammonium, z is from about 0.5 to about 2; and y is 1, this material having a ~agnesium ion exchange capacity of at least about 50 milligram e~. CaC03/9.
~ he aluminosilicate ion exchange builder materials are in hydrated form and contain from about 10~ to about 28X of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Hi~hly preferred orystalline aluminosilicate ion exchange materials contain from about 18X to about 22% water in their crystal matrix. The preferred crystall~ne aluminosil;-cate ion exchange materials are further characterized by a parti-cle size diameter of from about 0.1 micron to about lG microns.
Amorphous materials are often smaller, e.g., down to less than about 0.01 mioron. More preferred ion exchange materials have a particle size diareter of from about 0.2 micron to about 4 microns. The term "particle size diameter" represents the average particle size diameter of a given ion exchange material as deter-mined by conventional analytical techniques such as, for example9 microscopic determinat;on utilizing a scanning electron micro-scope. The crystalline aluminosilicate ion exchange materials arPusually further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC03 water hardness/g. of aluminosilicate, calfulated on an anhydrous basis, and which generally is in the range of from abou~ 300 mg.
eq./g. to about 352 mg. eq./g. The aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca~+/gallon/min-ut~/gra~/gallon of aluminosilicate ~anhydrous basis), and gener-ally lies w~thin ~he range of from about 2 grains/gallon/min-ute/gram/gallon to about 6 grains/gallon/~inute/gram/gallon, basedon calcium ion hardness. Optlmum aluminos~l~ca~es for builder ~,.

123'1326 - 4z purposes exhib~t ~ calc~um 10n exchange rate of at least about 4 gra1ns/gallon/minute/gram~gallon.
The amorphous alum~nos11~cate 10n exchange materials usually haYe a Mg exchange capac1ty of at least ~bout 50 mg. eq.
CaC03/g. (12 mg. ~9 /9.~ and a Mg exchange rate of at least about 1 grain/gallonlm1nute/~ram/gallon. Amorphous materials do not exhib1t an obser~lable d~ffraction pattern when examined by Cu radiat~on (1.54 Angstrom Un1ts).
Useful aluminos11icate ion exchange materlals are commercial-ly ava~lable. These aluminosilicates can be crystalline or amorphous 1n structure and can be naturally-occurring aluminosili-cates or synthetically deri~ed. A method for producing alumino-s111cate ion exchange materials is disclosed ~n U.S. Patent 3,9B5,669, i~rumnel, et al. 9 1ssued October 12, 1976. Pre-ferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designa-tions Zeolite~ A, Zeolite P (B?, and Zëolite X. In an especially preferred embodiment, the crystalline alumino-~ilicate ion exchange material has ~he formula Nal2~(Alo2)l2(sio2)l2] XH2 wherein x is from about 20 to about 30, especially about 27.
Other examples of detergency builders ~nclude the various water-soluble, alkal1 metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, s111cates, borates, polyhydroxysulfonates, polyace-tates, carboxylates, and polycarboxylates. Preferred are the alkal1 metal, espec~ally sodium, salts of the above.
Examples of su1table organic alkaline detergency builders include: (1) water-soluble amino carboxylates and aminopotyace-tates, for example, nitr~lotriacetates, glycinates, ethylenedi-amine tetraacetates, N-~2-hydroxyethyl)ni~rilo diace~ates and d1ethylenetriamine pentaacetates; (2) ~ater-soluble salts of phyt~c acid, for example, sodium and potassium phytatesi (3) wa~er-soluble polyphosphonates, includ~ng sodium, potassium and 35 11th1um salts of ethane~l-hydroxy~ d~phosphonic acid; sodium, potass~um, and lith1um salts of ethylene diphosphontc acid; and ,~ .

l ~d 3/ f~. 3 æ,f~

- ~3 -the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracar-boxylic acid, mellitic acid and pyromellitic acid; and (5)the water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495.
5pecific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, poly-meric metaphosphate having a degree of polymerization offrom about 6 to 21, and orthophosphate. Examples of poly-phosphonate builders are the sodium and potassium salts of ethylene-l,l-diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy~ diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,42~,137;
3,400,176 and 3,400,148.
Examples of nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbo nate, tetraborate decahydrate, and silicate having a mole ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
Useful water-soluble, nonphosphorus organic builders include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and poly-carboxylate builders are the sodium, potassium lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
~ lighly preferred polycarboxylate builders are dis-closed in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

.. ..
", ., L3Z~

Other builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
Other useful builders are sodium and potassium car-5 boxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxy-late phloroglucinol trisulfonate, water-soluble polyacry-lates (having molecular weights of from about 2,000 to about 200,000 for example), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal car-boxylates disclosed in U.S~ Patent 4,144,226, Crutchfield, et al., issued March 13, 1979, and U.S. Patent 4,426,495, Crutchfield, et al., issued March 27, 1979. These poly-acetal carboxylates can be prepared by bringing togetherunder polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
Another type of detergency builder material useful in the present compositions comprises a water-soluble material capable of forming a water-insoluble reaction produc~ with water hardness cations. This preferably occurs in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" compositions are fully disclosed in British Patent Specification No. 1,424,406.
Other useful detergency builder materials are the "seeded builder" compositions disclosed in Belgian Patent No.
798,856, issued October 29, 1973. Specific examples of such seeded builder mixtures are: 3:1 wt. mixtures of sodium carbonate and calcium carbonate having 5 micron particle diameter; 2.7:1 wt. mixtures of sodium sesquicar-bonate and calcium carbonate having a particle diameter of 0.5 microns; 20:1 wt. mixtures of sodium sesquicarbonate and calcium hydroxide having a particle diameter of 0.01 c~, . . .

iL2343Z~

- 4~ -micron; ~nd a 3:3:1 wt. mixture of sodium c2rbonate, sodium aluminate and calcium oxide having a particle dia~eter of S
microns.
Add~tional Op~ional Components Buffering agents can be utilized to maintain the desired alkaline pH o~ the bleaching solutions. Buffering agents include, without limitation, the detergency builder compounds disclosed hereln. Buffering agents su~table for use ~n the bleaching co~positions of the present ~nvention are wetl known in the detergency art.
Preferred optional ~ngredients ~nclude suds modifiers, parti-cularly those of suds suppressing types. These 1nclude, for example, silicones and s~l~ca~silicone mixtures. U.S. Patents 3,933,672, issued January 20, 1976 to Bartolotta et al, and 4,136~045, issued January 23, 1979 to Gault et al, disclose silicone suds controlling agents. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as slloxane having the formula:
~ R ~
~i2 ~ lx wherein x 1s from about 20 to about 2,000 and R and Rl are each alkyl or aryl groups, espec~ally methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes ~i.e., compounds of the above formula wherein R and R1 are methyl) having a molecular weight of from about 200 to about 2,000,000 (and higher~ are all useful as suds controlling agents. Additional suitable silicone materials where~n the s~de cha~n groups R and Rl are alkyt, ar~l, or mixed ~lkyt or ary1 hydrocarbyl groups, exhibit useful suds controllir,g propert~es. These include diethyl-9 dipropyl-, dibutyl-, methyl-, ethyl-, phenylmethylpoly-siloxanes, and the like. Additional usef~l s~licone suds controlling agents can be represented by a ~xture of an alkylated s~loxane, 25 refenred to hereinbefore, and ; solld s~l~ca. Such mixtures are prepared by affixing the silicone ,/?,, `

iZ39L3Z~;

to the surface of the solid sll k~. A preferred sil1cone suds controll1ng ~gent ~s represented by a hydrophobic s~lanated ~ost preferably trimethylsilanated) s~lka ha~/~ng a partiele size in the range fJom about 10 millim krons to 20 millim~crons and a S spec~fic surfaoe area above about 50 m2/gm~ int~ately admixed with d~methyl s~l kone fluid having a molecular ~e~ght ~n the range from about 500 to about 200,000 at a weight ratio of sil~-cone to silanated silica of from about 19:1 to about 1:2~ ~he s~l~cone suds suppress~ng agent is adYantageously releasably inoorporated in a water-soluble or water-d~spersible, substan-tlally non-surface-acti~e detergent-~mpermeable carrler.
Particularly useful suds suppressors are the self-emulsifying s~t1con suds suppressors, described 1n U,S. Patent 4,073,118, 6ault et al, issued February 21, 1978. An example of such a compound is DB-544, commercially available from Dow-Corning, which is a siloxane/glycol copolymer.
Suds ~odifiers as descr~bed above are used at levels of OX to about 2~, preferably from about 0.1 to about 1.5X b~ weight of the surfactant.
Microcrystalline waxes having a melting point ln the range from 35C-115C and a saponification Yalue of less than 100 represent addit1Onal examples of preferred suds eontrol components for use in the bleaching compositions of the present in~ention.
These are described in detail in U.S. Patent 4,056,481, Tate, 25 issued NoYember 1, 1977, incorporated herein by reference. The microcrystalline waxes are substantially water-insoluble, but are water-dispersible ~n the presence of or~anic surfactants. Pre-ferred microcrystatline wax~s haYe a ~elting point from about 65C
to 100C, a molecular weight in the range from 4~0-1,000, and a 30 penetration value of at least 6, measured at 77F by ASTM-D1321.
Su~t~ble examples of the above waxes include: ~icrocrystalline and oxidi2ed microcrystalline petroleum waxes; Fischer-Tropsch and oxidized F~scher-Tropsch waxes; o~okerite; ceresin; montan wax;
beeswax; candelilla; and carnauba wax.
Alky1 phosphate esters represent an additionat preferred suds control agent for use herein. These preferred phosphate esters 3~326 are predominately monosteary:L phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphate, which can contain di- and trioleyl phosphate.
Other suds control agents useful in the practice of the invention are the soap or the soap and nonionic mixtures as disclosed in U.S. Patents 2,954,347 and 2 ~ 954 r 348 ~
The following examples are given to illustrate the parameters of and compositions within the invention~ All percentages, parts and ratios are by weight unless other-wise indicated.
EXAMPLE I
The following bleaching/granular detergent composi-tions and systems were formulated using conventional procedures and techniques. When employed in conventional procedures for overall performance testing (such as that described in Example I of U.S. Patent 4,412,934, Chung, et al., issued November 1, 1983) or in typical washing procedures, excellent bleaching performance is obtained.
BLEACH COMPOSITIONS~SYSTEMS
A Sodi um perborate alone B Sodium perborate monohydrate Sodium 4-(2-chlorobutanoyloxo)benzene sulfonate 25 C Sodium perborate monohydrate Sodium 4-(2-chlorooctanoyloxo)benzene sulfonate D Sodium perborate monohydrate Sodium 4-(2-chlorononanoyloxo)benzene sulfonate E Sodium perborate monohydrate Sodium 4-(2-chlorodecanoyloxo)benzene sulfonate F Sodium perborate monohydrate Sodium 4-(3,5,5-trimethyl-2-chlorohexanoyloxo)-benzene sulfonate G Sodium perborate monohydrate Sodium 4-(2-chloro-2-ethylhexanoyloxo)benzene sulfonate H Sodi um per borate monohydrate Sodium 2-(2~chlorononanoyloxo)benzoate I Sodium perborate monohydrate ~Z~3~32~;

Sodium 4-~2-methoxydecanonyloxo3benzene sulfonate J Sodium perborate monohydrate Sodium 4-(2 methoxydodecanoyloxo)benzene sulfonate The following granular detergent compos1tion ~s prepared to 5 be used with the aboYe indicated systems and other bleach c~lpositions of the present invention:
Parts by Weight Sodium ~14 15 alkyl/alkylethoXY sulfate 8.75 C12-13 linear alkyl pri~ary alcohol ethoxylate 6 5T* 8.75 C12 alkyltrimethyl ammonium chloride 1.0 Sodium tripolyphosphate 37.0 Sodium diethylenetriamine penta-acetate 1.0 Sodium carbonate 14.0 15 Sodium sulfate 11.5 Silicon dioxide (SiO2) (1.6r) 6.0 ~ater 7.0 Bleach Composition C 12.0 Miscellaneous (e.g., perfumes, en~ymes, 20suds supressors, optical brighteners, etc.) 1.8 * Stripped of lower ethoxylated fractions and fat~y alcohol.
The abo~e granular detergent composition is used employing 12 parts of the bleach composition for each treatment at the suggested ratios. All ingredients of the final detergent co~position are added to the wash simultaneously. The overall order of addition is water - fabrics - test composition. In some cases, the activator may be Jissolved in water before addition.
Bleach Composition C in the detergent composition aboYe is replaced, in whole or in part, by Bleach Composi~ions D-J, or mix~ures thereof, and similar bleaching performance is obtained.
; Further, various ratios of perborate (total):bleach ac~ivator (total)9 by weight of the composition, may be empl4yed: 1:1, 3:1, 1:2, 1:3 and 6:5; good bleaching performance is obtained at these ratios for single systems, and for mixtures of such systems.
35The peroxygen bleach activator compounds of the above systems and Bleach Compositions are replaced, in part, by a second ;

~L23~3~

~3,9 conventional activator, at a ratio of alpha substituted peroxygen bleach activator:second actlvator of about 3:1 to ~bout 1:3. When such conventional acti~ator is selected from the group consisting of sodium 4~octanoyloxybenzenesulfonate; sodium 4 nonanoyloxy-benzenesulfonate; tetra acetyl glycouril; tetra acetyl ethylenediamine; and tetra acetyl methylene diamine, s~milar bleaching performance is obtained.
The sodium perborate monohydrate of the above Bleach Composi-tions and systems is replaced, in whole or in part, at a perborate (total):bleach activator ratio of abGut 1:3 to about 3:1, by one or more peroxygen bleach compounds selected ~rom the group con-sisting of sodium perborate tetrahydrate; sodium carbonate per-oxyhydrate; sodium pyrophosphate peroxyhydrate, urea peroxyhy-drate, and sodium peroxide; similar bleaching performance is ob-tained.
EXAMPLE II
Preparation of Bodies Containing Peroxygen Bleach ActiYator 87 parts of the selected peroxygen bleach activator ingredi-ent (alpha-substituted alkyl oxybenzene sulfonate) is thoroughly mixed with the binder or coating (Sorbitan monopalmitate) in a warm container 70-75C (160-170F) until a homogeneous doughy consistency is achieved. This mixture is then forced through a warmed 70-75C (160-170F) orifice ~approximately 1.5 mm diameter) to produce long noodles. After cooling to room temperature these are then cut into 1.5-3 mm lengths and screened (24 mesh) to remove fine particulate matter and dust resulting from ~he cutting operation. The final material is then added to, mixing thorough-ly, a granular de~ergent composition such as that described in j Example 1.
The binder material above is replaced, in whole or in part~
by C13LAS, Cl2LAS, C11bAS, sorbitan monolaurate, sorbitan mono-stearate, sorbitan monooleate, a 1:1 mixture (by ~eight) of PEG
8000:1auric acid, sodium polyacrylate and sodium methacrylate;
similar stability ls obtained.

~23~3~6 EX~MP~E III
Preparation of Disodium_p-Phenolsulfonate ~OC6H4S03Na-2H20 + NaOH 1--2 ~ NaOC6~4503Na 2) Dry Disodium p-phenolsulfonate was prepared by adding a solution of 483.5 9 ~12.1 moles) of sodium hydroxide in 75C ml of water to 2784 g (12.0 mole) of the monosodium salt dihydrate dispersed in 2 l. of water. The final pH of this ~ixture was 10.6. Most of the water was evaporated in a rotary evaporator and the resulting rigid solid was transferred to a vacuum oven for final drying at 115-120C (100 hours in this example). ~he anhydrous disodium salt weighed 2607 9 (99.6X yield).
Preparation of Sodium 4-(2-chlorooctanoyloxy)benzene sulfonate Anhydrous disodium p-phenolsulfonate ~221 9; 1.015 moles~ was slurried in 500 ml of dry diglyme (diethylene glyool dimethyl-ether) in a 1 1, three-necked flask equipped with a mechanical stirrer, thermometer and an inert gas inlet. This mixture was warmed to 48C and 200 9 (1.015 moles) o~ 2-chlorooctanoyl chlo-ride was added, dropwise or in a thin stream~ at such a rate that the temperature did not rise substantially abo~ 100C. The reaction mixture was cooled occasionally during the acid chloride addition. After the acid chloride had been added, the mixture was stirred for two hours at which time a thin layer chrom2togram and a proton nmr spectrum showed that the reaction was essentially complete.
~ he thick mixture was then diluted with ether ~o give an easlly pourable slurry which was filtered. The product (filter cake~ was reslurried in 1.5 l of ether and filtered again.
.. Recrystallization from 3.5 1 of 20~ aqueuus methano~ gave 280 9 (77~ yield) of sodium 4-(2-chlorooctanoyloxy)benzene sulfonate as lustrous white flakes. By thin layer chromatography~ infrared and nmr spectroscopy the product was virtually free of starting ~aterials or side products. Ele~en~al analysis ~nd kated it contained 0.44% NaCl.

~Z343Z6 - 51;
EXAMPLE lY
Prep ~ decanox~xy)benzene _~F~
Decanoyl chloride (19.1 9; 0.10 mole) was added all at once to a slurry of 21,8 9 ~0.10 mote) of anhydrous disodium 5 phenolsulfonate and 50 ml of dry monoglyme contained in a 500 ml round~bottomed flask protected from moisture. A modest exotherm occurred and the reaction mixture was stirred at ambient temperature o~erni~ht. A thin layer chromatogram indicated that the reaction was essentially complete, and the thick creamy mixture was diluted with ether and filtered. The solids were rinsed with additional ether, were sucked dry, and the product was then recrystallized from 500 ml of 10X aqueous mRthanol. The sodium pdecanoyloxybenzene sulfonate was collected by filtration and dried to give 34.6 9 (99~) of pearly flakes. Elemental, thin layer chromatographic, infrared and nuclear magnetic resonance analyses indicated that the product was essentially free of sodium chloride, starting naterials or other by-products.
XAMPLt V
Preparation of Sodium 4-(2-chlorononanoyloxyL~nzene sulfonate Anhydrous disodium p-phenolsulfonate (28.5 9; 0.130 ~ole) and 30.3 9 (0.1436 mole) of 2-chlorononanoyl chloride were combined in a 500 ml round-bottomed flask. The flask was then jmmersed in an oil bath which had been preheated to 110C. ~lthin fi~e minutes an exothermic reaction occurred ~hich caused the entire ~ixtur to congeal. After cooling, the mixture was triturated three times with 150-200 ml portions of ether and the produc~ was vacuum dried~ Elemental and nmr analyses of the resulting tan powder, 46.2 9, indicated that it was composed of 11.5~ NaCl, 17.7 disodium p-phenolsulfonate, and 70.8X of sodium p-(2-chloronona-noyloxy)benzene sulfonate. This represents a 68~ yield of the desired product.
EXAMPLE Yl Pre~ration of 2-Chloroalk~l Ac~d A one-liter, three-necked round bottom react~on flask was mounted in a fume hood and placed in a 335 watt hea~ing ~an~le. A
mechanical stirrer, dry ice condenser and a fritted gas dispersion .

:ILZ3g~3Z6 tube were fitted to the reaction flask. The temperature of the reaction flask was controlled by use of a Thermo-~atch which maintains the function of a Jack-0-Matic, upon which the heating mantle was placed. The dispersion tube was connected to a chlorine source by PYC tubing and metered with an in line flowmeter having a range of 0.05 to 1 li~er/min.
The reaction vessel was initially charged with 1.0 msle of stearic acid ~284.5 grams). The stearic acid was melted by raising the temperature to 80C. At this time 0.005 mole TCNQ
(1.02 grams) was added to the reaction vessel. Chlorine gas at a flow rate of 0.05 liter/min. ~as added to solubilize the TCNQ into the melted stearic acid. Acetic anhydride at a 0.06 molar level (6.125 grams) was then added to the reaction flask and the temperature was rapidly elevated to 130C. Using a pipette9 0.016 mole sulfuric acid (1.6 grams) was then added to the reaction vessel. The temperature was then adjusted to 150C and the chlorine flow rate was adjusted to 0.5 liter/min. ~his point was considered time zero for the beginning of the reaction.
After 52 minutes of reaction time, the chlorine flow rate was readjusted to 0.05 liter/min. and the reac~ion mixture was slowly cooled under a head of chlorine gas to the product melting point (64C) After cooling, the reaction product was analyzed by gas chromatography as being 96.lZ~ 2-chlorostearic acid, 2.71 2~2-dichlorostearic acid, 0.42X free radical chlorination products, and 0.75X unreacted stearic acid.
If the above reaction is carried out with fatty acids having alkyl chain lengths from 8 to 18 carbons, or combinations thereof, j the corresponding 2-chloroalkyl acids are produced in purities exoeeding 95~. These materials may then be employed as follows:
Preparation of 4-(2-chlorononanoyloxy~ben~enesulfonate The reaction was carried out in a 12 l flask equipped with a heavy duty paddl e s~i rrer, reflux condenser, addi ti on funnel, thermometer, heating mant~e and inert gas inlet.
A slurry of 2237 g (10.26 moles) of disodium p=phenolsulfon-ate ~n a gallon of dry 1,2-dime~hoxyethane (~onoglymR) was warmed ~L2343216 to 50C. The heating mantle was switched off and the addition of 2169 9 (10.28 moles) of 2-chlorononaoyl chloride was begun. The rate of addition was such that a steady rPflux was maintained. As the reaction proceeded, it thickened and after 80 minutes, with about 80-85~ of the acid chloride added, another 500 ml of solvent was added to improve stirring. The acid chloride addition was complete within 1.5 hours after which the mixture was allowed to stand overnight.
Ether (3 l) was added to gi~/e a thinner slurry and the crude product was collected by ~acuum filtration. ~y nmr, the crude product contained 88 mole percent product and 12 mole percent starting phenolsulfonate (plus salts~.
Recrystallization was carried out, batchwise, from a total of 65 l of 12.5% aqueous methanol at 5C. There was obtained 2672 9 (70X yield) of first crop product as lustrous white flakes.
Concentration of the ~other 1iquor followed by another recrystallization ga~le a second crop (330 9) which brought the recovered yield to 79X.
EXAMPLE V l l A base detergent product was prepared with the following composi ti on:
Base Product -Sodium Cl4 15 alkyl sulfate 7 5 Sodium C13 linear alkylbenzene sulfonate 7.5 C12 alkyltrimethyl am~onium chloride 1.0 C12-13 alkyl polyethoxylate6 5T 1.0 Sodium silicate 5.0 Sodium tripolyphosphate 32.0 Sodiu m s ulfate 11. 2 3~ Sodium carbonate 16.0 Miscellan eou s ( e . g ., perfu me , optical brightener, protease enzyme, suds suppressor, chelating agent, polyethylene glycol, etc.) ~alance Various mixtures of the activa~ors sodium 4-nonanoyloxy-12343Z~

benzene sulfonate and sodium 4-(2-chlorononanoyloxy)benzene sulfonate ~hereinafter NOBS and alpha-chloro NOBS) were added along with the peroxygen bleach compound, sodium perborate monohydrate (hereinaFter PB13, to the base detergent product in S the amounts ~ndicated below. ~he result~ng detergent products were then tested in full scale washers, using 150û parts per million- (ppm) of product, a water temperature of 95F (35~C) and a water hardness of 5 grains per gallon, respec~iYely.
A panel of expert graders compared the cleaning performance 10 of the products on selected stains using a scale in which O Ineans "There is no difference"; 1 means "I think I see a difference"; 2 means "I see a difference"; and 3 means "I see a b~g difference".
The results in average panel score units (PSU) versus a zontrol, which contains 4~ N08S and 3.5% PB1, were as follows:
80:20 alpha- 60:40 alpha-alpha-Chloro Chloro IIOBS: Chlo~o NOBS:
Activator N O B S N O B S N O B S L~5 Activ. Level 4.0~ 4.0X 4.0X
PB1 Level 3.5g 3.5% 305X
_ _ _ _ _ _ _ Stain PSU grades vs. 4X NOBS / 3.5X PB1 Dingy 0.1 û.1 -0.1 0.56 T -shirts Din gy O . 2 0 . 2 -O .1 0 . 62 pillow cases Carrot juice -3.4 -2.3 -1.3 1.52 Barbeque -3.1 -1.9 -1.3 1.89 Spaghe~ti -1.4 -1.3 -0.8 2.25 60:40 alpha-40:60 alpha- 20:80 alpha-Chloro NOBS: Chloro NOBS: Chloro NOBS:
Activator NOBS _ NOBS _ NOBS_ _ LSD~
Activ. Level 4.0X 4.0% 4.0X
PB1 Level 3.5~ 3.5% 3.5X
-----_--_- -__ _-__- ___ _ _______ __ ______ ~;~34326 5~
Sta~n PSU grades vsO 4X NOBS / 3.5X PB1 Dingy -0.1 0.2 -0.3 0.68 T -shirts Pfllow -al. 1 O. O 0. 1 0 . 52 cases Carro~ juice206 -1.7 -1.1 2.19 Barbeque -1.3 -0.9 -0.4 2.57 Spaghetti 0.4 -0.2 0.5 2.65 As shown above" mixtures of alpha-chloro NO~S
10 and NOBS provide effective bleaching.
EXAMPLE VIII
The base product and testing condi~ons were as per Example VII. The amount ~f perborate was varied to show the effect of reducing perborate usage at constant mixed NOBS activator levels.
60:40 alpha- 60:40 alpha-Chloro NOBS: Chloro NOBS:
Activator N O B S N O B S _ ~95 Activ. Level 4.0~ 4.0X
20 Per~orate Level 3.5X 2.7%
___________ __ _ ___ __ _________ ___ _ __ ___ _ _ _________ _ Stain PSU vs. 4~ NOBS / 3.5~ PBl Dingy ~.2 -0.1 0.64 T -shirts P~llow _ _ _ cases Carrot juice-0.8 -1.4 1.36 B arbeq u e-1. 4 -O . 7 1 . 35 S pa g het~-0 . 2 -0 . 5 1.10 60:4D alpha- 60:40 alpha- 60:40 alpha-Chloro NOBS: Chloro NOBS: Chloro NO~S:
Acffv~tor NOBS _ NOBS _O~S _ ~5 Ac~v. Level 4.ûg 4.0X 4.0X
PBl Level 3.5X l.9X 1.0 ____ ____________ _________________ ___ ________________ __ _ _ , ... . ,", j~, ~ .

~2343Z6 - 5~ -Stain PSU grades vs. 4~ NOBS / 3.5g PBl Dingy -0.1 0.1 -0.3 0~29 T-shirts Dingy 0.1 ~0.3 -0.2 0.4B
pillow cases Oarrot juice -2.6 -2.3 -2.2 1.41 Barbeque -2.1 -1.6 -1.0 l.9g Spaghetti ~0.3 -0.7 -103 3.09 As shown aboYe, the 60:40 alpha-chloro mixed actiYator shows lO effective bleaching e~en when the perborate levels are reduced significantly.
EXAMPLE IX
An odor profile evaluation of alpha-chloro NOBS, NOBS, and mixed NOBS was performed by trained perfumers.
The base product of Example ~II was used. The peroxygen bleach compound and varying activator mixtures were added as indicated below, and the resulting detergent products were tested ; in automatic mini washers using 1500 ppm of product at watertemperature of 125F ~52C~ and a water hardness of 5 grains per gallon, respectively. Soiled fabrics were ad~ed to the wash any special conditions are noted below.
Odor profiles were then evaluated by trained perfumers, who ranked them from 1 to 5 in order of preference.
Treatment: 1 - 100~ alpha-chloro NOBS
2 - 80:20 alpha-chloro NOBS:NOBS
3 - 60:40 alpha-chloro NOBS:NOBS
4 - 40:60 alpha-chloro NOBS:N08S
5 - 20:80 alpha-chloro NOBS:NOBS
~, 6 - 100~ NOBS

.. . .

123~3Z~

Test #l (Special condition: No soiled fabrics added) .
Treatment ~ Odor Characterist~cs 1 1 Light sweet odor, very clean overall 2 2 Light sweet odor, clean overall 3 3 Best balance between treatments 1 ~ 6, some fatty, bleachy odor 4 - Not tested 4 Fatty bleachy odor o 6 5 Strongest fatty bleach odor of series Test #2 Treatment Ranking Odor Characteristics 1 3 Clean, slight sweet note 2 5 Sour chemical, oily, alpha-chloro odor 3 2 Clean, slight chemical, oily odor 4 1 Cleanest of series - Not tested 6 4 Fatty, bleach odor : Test #3 .
Treatment Rankin~ Odor Characteristics .
1 5 Poor overall, too much of dirty alpha-chloro odor 2 - Not tested 3 3 Alpha-chloro odors initially, but dissipated quickly : 4 1 Very good overall, clean9 no bleach odors 2 Good overall, some bleachy but : much more acceptable ~han #6 6 4 Typical bleach odor, sour, fatty 12343,',2G

Test #4 (Special conditions: 95F (35C) Treatment ~ Q ~ t~5 1 4 Dirty alpha-chloro odors (i.e.9 sweet), strong soil odor 2 - Not tested 3 1 Clean, trace of a1pha-chloro .............. ............. ... ... ........... odor, good overall 4 2 Same as ~3 Strong bleach and alpha-chloro odors, poor overall 6 3 Bleachy odor, soil odors presen~9 typical As demonstrated above, the mixtures consistently show better odor profiles than 100% NOBS. Under soil conditions, they also show better odor profiles than 100% alpha^chloro NOBS.
The foregoing illustrates the use of various conventional fabric laundry detergent ingredients such as conventional deter-sive surfactantst builders, suds control agents, enzymes, bleach-es, and the like, with the bleach activator compounds and compo-sitions of this invention.
The following examples are typical of detergent compositions,again with conventional detersive ingredients, and formulated especially for use under European laundering conditions, although they may be used to advantage under all conditions9 especially in front-load~ng automatic washing machines.
The composition of Example X is of spec~al interest, since it contains a clay fabric softening agent. Such clay softeners are well~known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included ~mong such clay softeners are various heat-treated kaolins and var~ous multi-layer smectites. Preferred clay so~teners are smectite softener clays that are described ~n German patent document 2 334 899 and in U.K. Patent 1 400 898 which can be referred to for details. So~tener clays are used in the preferred 3~ granular detergent compositions at levels of a~ least 1~, gen erally 1-20~, preferably 2-7%.

3~3ZÇi It ~s to be understood that the use of typ~cal alkoxylated nonionic surfactants (e.g. the Cg-Cl8 alkyl alcohols and alkyl phenols with S to 20 ethoxyl groups) preferably should be limited in the practice of this ir,vention to levels of not more than about - 5X, generally not more than 2X, most preferably O-IX, of the compositions when clay is present as a softener, since alkoxylates can interfere with the softening properties o~ clay. In clay-free co~positions, the alkoxylated nonionics can be used at any desired level.
EXAMPLE X
An aqueous crutcher ~ix comprising the following ingredients is prepared and spray-dried in standard fashion (percen~ages listed relate to percent ingredients in the complete ~ormulation after spray-drying).
Ingredients Percent C11,12 alkyl benzene sulfonate 6.~
Tal~ow alcshol ethoxylate (EOll) 1.0 Sodium perborate 2000 Sodiu~ tripolyphosphate 24.0 Sodium sulfate 22.0 Sodiu~ silicate 8.0 Smectite clay ~ 2.4 Ditallow methyl amine 3.8 Carboxymethyl cellulose O.4 Enzymæs (amylase/protease mix) O.S
Opt~cal br~ghtener 0.?3 Sulphonate~ zinc phthalocyanine ** 25 ppm EDTA 0.2 Perfume/copper salts/minors/brightener 0.5 Suds suppressor 2.7 Mois~ure to IOO
* Natural smectite; CaC03 ion exchange capacity above 50 ; ~eq/1009 clay ** U.S. Patent 3 927 967 After spray-drying, bleash bodies prepared in the manner of Example II and comprls~ng so~um 4-(2chlorononanoyloxy) benzene 123~3ZG

sulfonate ("alpha-chloro NOBS") are dry-blended with the composi-tion. The total alpha chloro NOBS content of the final granules is 5% by weight.
The composition of Example X may be modif~ed by the addition 5 of 1-3% pentacetyl glucose as an auxiliary bleach act~vator.
EXAMPLE XI
A nil-P spray-dried detergent formulation i5 as follows:
In~redient Percent Zeolite A (1-10 micron) 26.0 Sodium nitrilotriacetate ~.D
Cll 12 alkyl benzene sulfonate (Na) 6.5 Tallow ethoxylate (EO 9-11) 3.5 Sodium perborate.4H20 20.0 Sodium silicate 8.0 CMC 1.0 Sodium sulfate 20.0 Enzymes (1:1 amylase/protease) 1.5 Optical brightener 0.5 Bleach activa~or * ~.0 Water, minors to 100 * Sodium 4-(3,5,5 trimethyl 2-chlorohexanQyloxy)benzene sulfonate The composition of Example XI is prepared by spray-drying an aqueous crutcher mix, then dry-mixing in the bleach activator component.
It will be appreciated that the bleach ~ctivators and bleach-ing compositions of th~s invention may be conveniently packaged in pre-measured form; for example, in pouches, bags, sachets, or the ke, which may be made of water-soluble or water-permeable materials, or which are designed to open due to heat or mechanical action during a laundering operation. Apprspriate containers are widely disclosed ~n the literature, and usually contain from 1-120 gra~s of composition.
: In another mode9 the bleach activators herein can be water-releasably affixed to a par~iculate substrate; a sheet-~orm substrate is especially convenient. In-use, the sheet is added to , , 123~3;Z 6 an aqueous laundry liquor containing a peroxide source ~perborate is commonly used), whereupon the activakor ~s released from the substrate to perfon~ ~ts intended function. Such sheet-form products will generally employ 1-20 grams of acti~ator per sheet.
EXAMPLE XII
A laundry additive product ~s prepared by warming 6.5 9 of tallow trimethyl ammonium chloride and spreading the melt onto an ordinary disposable paper hand-towel (20x20 cm). 4 grams of alpha-chloro NOBS powder (1-10 microns) are sprinkled onto9 and pressed ~nto, the melt before it has the chance to solldify.
The article of Example X~I is added to a laundry liquor containing a commercial perborate~clay detergent composition (DASH-3; Trademark) to enhance through-the-wash bleaching perfonm-ance.
As can be seen from the foregoing, the present invention provides means for bleaching ~abrics which, ~n general termsl involves contacting soiled or stained fabrics wi~h the composi-t~ons herein in the presence of water. Usually, the compositions are present at levels of 100-2000 ppm of the water, but higher or lower levels can be used, depending on the degree of soiling and staining.
SJG/jmc~APP:A61)

Claims (17)

1. A body containing a stabilized, particulate bleach activator comprising:
(a) from about 50% to about 99.5%, by weight of said body, of a bleach activator compound of the general formula where R is a straight or branched alkyl or alkenyl group having from about 4 to about 14 carbon atoms, R1 is H or C2H5, X' is Cl, OCH3 or OC2H5 and L is a leaving group se-lected from wherein R2 is an alkyl chain containing from about 1 to about 8 carbon atoms, and Y is -SO3-M+ or -COO-M+ wherein M+ is sodium or potassium; and (b) from about 2% to about 50% of a binder material selected from the group consisting of nonionic surfactants, poly-ethylene glycols, anionic surfactants, film forming polymers, fatty acids and mixtures thereof wherein said binder does not melt below about 40°C;
wherein (a) and (b) are substantially evenly distributed through-out said body, the density of said body is above about 1.06 g/cc and said body contains less than about 5% water.

2. A composition according to Claim 1 wherein the level of activator is from about 50% to about 98%,and wherein the level of the binder is about 0.5% to about 50%, by weight of the body.

3. A composition according to Claim 2 wherein the level of activator is about 85% to about 96%, and wherein the level of the binder is about 4% to about 15%, by weight of the body.

4. A composition according to Claim 1 wherein said body is prepared by radial or axial extrusion.

5. A composition according to Claim 1 wherein the binder material is a nonionic surfactant.

6. A composition according to Claim 1 wherein the binder material is a polyethylene glycol having a molecular weight of from about 2,000 to about 15,000.

7. A composition according to Claim 1 wherein the binder material is a fatty acid.

8. A composition according to Claim 1 wherein the binder material is an anionic surfactant.

9. A composition according to Claim 1 wherein the binder material is a film-forming polymer.

10. A composition according to Claim 1 wherein the binder material is a mixture of fatty acids and nonionic binder materi-als.

11. A composition according to Claim 1 wherein the binder material is selected from the group consisting of water soluble linear alkylbenzenesulfonates in which the average number of carbon atoms in the alkyl moiety is about 11 to about 13;
aliphatic alcohols containing about 9 to about 18 carbon atoms and ethoxylated with and average of between about 40 to about 80 moles of ethylene oxide per mole of alcohol; sodium polyacrylate; sodium methacrylate; polyethylene glycols having a molecular weight of from about 4,000 to about 8,000; fatty acids containing from about 12 to about 18 carbon atoms; and mixtures thereof.

12. A composition according to Claim 1 wherein the density of said body is above about 1.08 g/cc.

13. A composition according to Claim 12 wherein the density of said body is from about 1.10 g/cc to about 1.30 g/cc.

14. A body containing a bleach activator comprising by weight:
(a) from about 50% to about 99.5% of a peroxygen bleach activator compound having the general formula wherein R is a straight or branched chain alkyl or alkenyl having from about 4 to about 14 carbon atoms; R1 is H or C2H5, X' is Cl, and L is selected from the group consisting of O SO3-M+ and O CO2-M+ wherein M is sodium or potassium; and (b) about 4% to about 15% of a binder material selected from the group consisting of sorbitan fatty acid esters, ethoxy-lated varieties of these sorbitan esters having an average total level of ethoxylation of from about 4 to about 8 moles of ethylene oxide per mole of sorbitan; linear alkylbenzene-sulfonates in which the average number of carbon atoms in the alkene moiety is about 11 to about 13; aliphatic alcohols containing between 9 and 18 carbon atoms ethoxylated with between 40 and 80 moles of ethylene oxide; sodium poly acrylate; polyethylene glycols having a molecular weight of from about 4000 to about 8000, fatty acids containing from about 12 to about 18 carbon atoms; and mixtures thereof; the density of said body is from about 1.10 g/cc to about 1.30 g/cc, and said body contains less than about 1.5% water.

15. A bleaching composition comprising, by weight, (a) about 0.5% to about 40% of bodies according to Claim 14;
(b) about 1% to about 60% of a peroxygen bleaching compound capable of yielding hydrogen-peroxide in an aqueous solution; and (c) about 1% to about 30% of a detergent surfactant.

16. A composition according to Claim 15 wherein said bodies have a particle size distribution of from about 50 microns to about 2.5 millimeters and wherein no more than about 5% of the bodies are greater than about 2 millimeters.

17. A composition according to Claim 16 wherein (a) within said composition is from about 300 microns to about 1.5 millimeters.