Note: Descriptions are shown in the official language in which they were submitted.
CA 02205412 1997-05-15
WO 96J16155 PCT/US95/14687
t BLEACHING COMPOSITIONS AND BLEACH-ADDITIVES
COMPRISING BLEACH ACTIVATORS EFFECTIVE AT LOW
sPERHYDROXYL CONCENTR~TIONS
FELD OF T~ INVENTION
The present invention relates to improved compositions colllplisLng bleach
activators. The bleach activators ~hAI~ce or boost the pt;lrol,..ance of blea~hing
agents such as perborate. The bleach activators are useful in fabric laundry andlS bl~achin~ co~n~os;~ionc~ automatic dishwashing colllpos;~;one hard surface .,I~.e.s,
bleach additives and the like.
BACKGRQUND OF THE INVENTIQN
The formulation of detergent cGn.l)osilions which effectively remove a wide
variety of soils and stains from fabrics under wide-ranging usage col-~;l;o~e remains a
20 considerable ch~ nge to the laundry dele.~nl Lldusll~. ChQlle~es are also faced
by the formulator of ~ O,..~;C di~h~l~g det~g~,.ll comroeitions (ADD's), which
are ~,Apeclcd to eR;~ iertly cleanse and sanitize d;sh~" o~en under heavy soil loads.
The problems ~eeo~ ted with the form~ ti~n of truly effective cle~ni~ and
b'e~hine CO...pG~.I;QIlc have been exac~.l,aled by legicl~tiQn which limits the use of
2s effective LlgredicllLs such as pho~l,h~te builders in many regions of the world.
Most CGI~ n~l C~ B comro~eitione contain mixtures of various detersive
surfactants to remove a wide variety of soils and stains from surfaces. In ~d~litiQn~
various detersive el~..~s, soil sl~cpf~n~ g agents, non-~hos~ho~us builders, optical
t~vn~ and the lilce may be added to boost overalt cl~A";~ p~,-rulll~ance~ Many
30 fully-formul~ted ~.k~n: ~8 compositions contain oxygen bleach, which can be ap~.bulale or pc~c~l,onà~e co~npolJn~ While quite effective at high t~iu.p~lalur~s,
p~,.bGIales and p.,.~all,onàtcs lose much of their bleaching rm.~l;Qn at the low to
moderate tcmpc.~lures L.c~as~ favored in CQ~ mf- product use. Accordi,lgl~,
various bleach a~ atols such as t~ yl~,tll~t~ ~ed:-mi~r (TAED) and
3s nol~loyloA~ lrol~-le (NOBS) have been dcveloped to polP~ f~ the
b'o~hi.~e action of p~bùlale and pe~c~l,onà~e across a wide t~.llp~,.al~l-c range.
NOBS is particularly effective on "dingy" fabrics.
CA 0220~4l2 l997-0~
WO 96/16155 PCT/US95/14687
A limitation with activators such as the widely commercialized TAED is that
the wash solution or liquor should have a pH of about 10 or higher for best results.
Since soils, especially from foods, are often acidic, detergent products are frequently
quite alkaline or are buffered s~lfficiently to ~ ;tl a high pH so the bleach
s activator system can operate effectively throughout the wash. However, this need
runs counter to providing milder formulations which could be improved in their
cG~ .alibility with fabrics, glassware and/or skin. In cle~nin~ operations below pH
10, many of the existing bleach activators lose their effectiveness or undergo
compe~ g side reactions which produce h~e~l~Liv-e byproducts.
The search, thelt;l~re, continues for more effective activator materials,
especially for use in mildly alkaline washing liquors or with decreased levels of
pe~l,u~te or other sources of hydrogen peroxide. Improved activator materials
should be safe, effective, and will preferably be decigned to interact with troublesome
soils and stains. Various activators have been described in the literature. Many are
15 esoteric and e,.l.el.~ive.
It has now been determined that certain sçlecled bleach a~,Liv~Lo-~ are
unexpectedly effective in removing soils and stains from fabrics and hard surfaces
such as dishes even under low alkaline wash con~itionc or with decreased levels of
hydrogen peroxide. These activators also have adv~nt~geo~ y high ratios of rates of
20 pe~llydlolysis to hydrolysis and of perhydrolysis to diacylperoxide fo.."aLion.
Without being limited by theory, these unusual rate ratios lead to a number of
.~ignific~nt benefits for the instant activators, incl~ltli~ increased çffi~ nny~ avoidance
of wasteful byproduct formation in the wash, incltased color con~ ibility~ cl~sed
enzyrne co",l)alibility, and better stability on storage.
When formul~ted as described herein, dele.~,~,nL co..... po~iLions are provided
using the sele~iled bleach activators to remove soils and stains not only from fabrics,
but also from dishware in a~.~o...AI;c di~hw~sl ing co..,pos;l;Qn~ from kitchen and
bal},.oom hard surfaces, and the like, with PYceilPnt results. The activators are
dç~i~çd to function well over a wide range of washing or soaking te""~e.alu.t;s and
30 are coml.~ le with rubber surfaces, such as those of sump hoses often used inEuropean front-loading washing m~hinPs In short, delelge.,L composilions herein
provide a ~ubsLanLial advance over those known in the art, as will be seen from the
di~closures hereinafter.
BACKGROUND ART
-
CA 0220~412 1997-o~
WO 96/16155 PCT/US95/14687
Bleach activators of various types are described in U.S. Patents 4,545,784;
4,013,575; 3,075,921; 3,637,339; 3,177,148; 3,042,621; 3,812,247; 3,77~,332;
4,778,618; 4,790,952; EP 257,700; WO 94/18299; WO 94/18298; WO 93/20167;
WO 93/12067; and in JP 02115154. Other references include Aikawa CA 85: 1086z;
s Stçhlice~ CA 108:187402w; Ishida CA 88:169981y; Kirk Othrner, Encyclopedia ofChemical Technology, Vol. 7, 4th Ed., 1993, pp. 1072- 1117; Kirk Othmer,
Encyclopedia of Chemical Technology, Vol. 4, 4th Ed., 1994, pp. 271-299; Kirk
Othmer, Encyclopedia of Chemical Technology, Vol. 9, 4th Ed., 1993, pp. 567-620. SIJ~IARY OF THE ~NVENTION
0 The present invention relates to bleach-additive or bleaching compositions
suitable for the dome~tic trr~mrnt of fabrics or hard surfaces. The compositions of
this invention can further comprise a source of hydrogen peroxide, and also include
embo~imrnts which are subst~nti~lly free from hydrogen peroxide or hydrogen
peroxide rele~i~ sources.
The cle~ning compositions herein comprise an effective amount of one or more
pe,rol,.lal1ce-enh~nced bleach activators. These activators are selected to haveparticular properties so that they are more effective in promoting bleaçhin~ under
certain use conditions in which TAED or similar conventional bleach activators are
relatively inefficient and ineffective.
In general, suitable activators for the present cle~nin~ compositions co",p,;se
one or more moieties RC(O)- which produce a peracid RC(O)-OOH on
perhydrolysis (reaction with perhydroxyl, -OOH). R is selecled such that the
dilTelence in aqueous PKa bel~een acetic acid and the carboxylic acid analog,
RC(O)OX of said peracid is at least 0.6, prefe.~ly at least about 1.2. When it is
2s stated that the di~.ence in flqueo~s PKa b~-.cen acetic acid and the call~ur~y-lic acid
analog, RC(O)OH, of a peracid is at least 0.6, the following subtraction, in the cfited order, is made: PKa (CH3C(O)OH) - PKa (RC(O)OH).
These pc.rullll~ce enh~nred bleach activators also have a low pH
p~,.h~drulysis e~l~,;cn~ coeffiriPnt (a practical measure of peracid fc,.-..~lion further
defined hereinafter) of greater than about 0.15, preferably greater than about 0.3,
and a ratio kp/kD > 5, more plefe.dbly kp/kD 2 30, still more preferably lcp/l~D >
50, wherein 1~ is the rate con~nl for p~.hydrolysis of the p~,rul"lal~ce-f-nh~nr,ed
bleach activator and kD is the rate con~t~nt for the formation of a diacylperoxide,
RC(O)OOC(O)R, from the pelrul,n~llce-enh~n~ed bleach activator.
CA 0220~412 1997-0~
WO 96/16155 PCT/US95/14687
.
The activators herein preferably comprise one or more moieties, L, which act
as leaving groups on perhydrolysis. Thus, preÇe.,ed pe~ru~ dl1ce çnh~nced bleachactivators herein have the formula RC(O)-L.
P-t;r~--ed leaving groups, L, co--.~-ise at least one tri-coordinate nitrogen atom
5 covalently connecting L to RC(O)-. Furthermore, the plere..~d pe.rù--..ance-
P ~h~l~r,ed bleach activators are capable of forming a maximum of one mole
equivalent of said peracid on perhydrolysis and have kH s 10 M-l s-l and a ratiokp/kH ~ 1, more preferably kp/kH 2 2, wherein kH is the rate con~l~.L for
hydrolysis ofthe p~.ro....ance-enh~nr,ed bleach activator and kp is said rate coo for perhydrolysis.
In general, R and L can independently be neutral or can be charged either
positively or negatively. In prere..ed compositions, both R and L are neutral
whe~ L is typically selected from suitably s~.hstituted or unsubstituted l~ct~m~, 2-
alkyl 4,5- dihydroimid~701.os, and mixtures thereof, and R is illustrated by p-
15 nitrophenyl or, more preferably, an alkylsulfonylphenyl moiety. Suitable R I cietie~are illustrated at length herein~ler.
In pl~r~..ed embo~iments, R can be connected to -C(O)- through a carbon
atom which forms part of an aromatic ring, and L can be selected such that its
co~ g~tP acid, HL, has an aqueous pKa in the range from greater than about 13 to20 less than about 17.
In other highly p.ere..ed embodim~nt~ the pwru~ al1ce-enh~nr,ed bleach
activator as a whole, or simply its leaving group, L, is free from any heterocyclic
moiety wl-e- t;ll a hydrogen atom is ~tt~cl-ed to a carbon atom that is alpha to both a
carbonyl group and a multivalent heteroatom.
2s The compositions of this invention may include additional de~ergc.. ~ additiws
inrl~l~ling one or more of the following ingredients: surf~rt~ntc low-fi7~ g
..ulo~ ic dl~llvvaslling surf~ct~nt~, ethoxylated nonionic surf~ct~nt~, bleach stable
thickeners, tr~ncition-metal cl~f~ , builders, floulesce..~ wl.;~ g agents (alsoknown as brigl~ ), and bu~li~lg agents. Compositions of this invention are
30 typically forrn~ ted below drycle~rling-useful levels of any organic solvent.Pl~r~,~bly the compositions are ~ubs~Lially free from organic solvents. Plere.,~,d
builders are sele~,led from the group co~.cictin~ of citrate, layered silicate, zeolite A,
zeolite P and mixtures thereo
A typical bleach-additive co"~posiLion herein co".~..iscs.
CA 022054l2 l997-05-l5
WO 96/16155 PCT/US9S/14687
(a) from about 0.1% to about 30% of said pelro,lllallce-~nh~nced bleach
activator;
(b) from about 0 1% to about 60% of nonionic surfactant; and
(c) from about 0.001% to about 10% of a transition-metal chelant.
s A typical blP~chin~ composition herein comprises:
(a) from about 0.1% to about 30% of said performance-enh~nced bleach
activator;
(b) from about 0.1% to about îO% of a hydrogen peroxide source; and
(c) from about 0.001% to about 10% of a trancitio~-metal chelant.
0 In plcrelJed emboriiments, the bleaching compositions deliver an aqueous pH
in the range from about 6.5 to about 9.5, more preferably from about 7 to about 9,
still more preferably from about 7.5 to about 8.5, and the level of source of hydrogen
peroxide is s~lfficient to provide a perhydroxyl ion concentration, as measured at a
pH of about 7.5, of about 10~ to about 10-1 molar, more preferably about 10-5 to
about lo-8 molar.
Additional illustrations of the bleach-additive or ble~hin~ compositions
enco...l.~csed herein are those colnplisillg from about 0.1% to about 10% of a
pwro--lldnce-enh~nced bleach activator selectçd from the group co~ .g of:
p-nitrobenzoyl caprolactam; p-nitrobenzoylvalerolact~m; linear or branched C2-Cg20 alkylsulf~nylbcnzoylcaprola~t~m; linear or l,l~ched C2-Cg alkylsul~l.yll,en~oyl-
valerol~ct~m, linear or ~lanclled C2-Cg alkyloxysul~..yll,c.~oylcaprolactam; linear
or blanched C2-Cg allyloxysulfonylbenzoylvalerol~ct~m; linear or b.anched C2-Cg
alkyl(amino)sulf~..yll,~,.~oylcaprolact~m; linear or b.a.1clled C2-Cg alkyl(amino)sul-
fonylbenzoylvalerolact~m; 2-furoylcaprol~ct~m; 2-furoylvalerol~ct~m; 3-furoylcapro-
2s lactam; 3-furoylvalerolactam; 5-nitro-2-furoylcaprolactam; 5-nitro-2-furoylvalero-
lactam; l-naphthylcaprolactam; 1-naphthylvalerolactarn; and mixtures thereof. More
pleferably in these embQdim~ntc, the p~;lru--..ance-enh~nced bleach activator is~elecled from the group con~istin~ of linear or blanclled C2-Cg alkylsulfonyl-
benzoylcaprolact~m; linear or blallclled C2-Cg alkylsulro,.~lbenzoyl-valerol~^t~m;
30 linear or b~ncllcd C2-Cg alkyloxysulfonylbenzoylcaprol~ct~m; linear or branched
C2-Cg alkyloxysulfonylbenzoylvalerolactam; linear or branched C2-Cg alkyl(amino)-
sulfonylbenzoylcaprol~^t~m; linear or b~anched C2-Cg alkyl(amino)sul~-.,~ll,c,~l-
valerol~ct~m; 2-furoylcaprolart~m; 2-furoylvalerol~t~m; 3-furoylcaprol~ct~m; 3
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
furoylvalerolactam; S-nitro-2-furoylcaprolactam; 5-nitro-2-furoylvalerolactam; and
mixtures thereof.
In highly p,ere,led embo~imentc~ these compositions further comprise a bleach
catalyst at the art-~icrlosed levels. Such compositions have particularly .ci~nific~nt
5 bk,~-hi~ pe,ru""allce enh~l~ce.~.e.~ as co",pared with otherwise idPInti~
compositions in which a convçntion~l bleach activator such as TAED is used in place
ofthe pc.~ll"ance-P;~-h~l-ced bleach activator.
This invention also relates to novel, pelrullllallce-enh~nced bleach activator
compounds having the formula RC(O)-L, wl,t,~;hl L is selected from the group
0 cons;sl",g of lactams and 4,S-dihyd~oi~idazoles; R is sPIPcted from the group
con.C~c~ g of s~bstituted phenyl having more than one chloro, bromo or nitro
substitllPnt; furan or substituted furan having one or more chloro, bromo, nitro,
alkylsulfonyl or arylalkylsulfonyl substituentc; l-naphthyl; substituted 1-naphLl,~yl; or
substituted 2-naphthyl having one or more chloro, bromo or nitro substituçntc;
O
R~ A~o--
0=~=0 , O=S=O
Rl ~,1
lS - -b - -b
and ~ e5 thereof;
wl~e~ei~l in each structure a is independently 0 or 1, b is 0 or 1, and A is sPle~ed from
O and NR2 wL~,.ein R2 iS H or methyl; and ~h~;rein when a is 1 and A is O, R1 issple~(p~d from alkyl, arylalkyl, alkoxy, a-yloxy, alkylamino, and arylamino; when a is 10 and A is other than o, Rl is selected from alkyl and arylalkyl. Compositions
these novel compounds are also in~ ded in the scope of this invention.
The invention also PnCo~paccp~s a method for removing stains from fabrics or
hard surfaces, espe~ ;~lly disl,~v~t;, comprising cont~cting said stains with a source of
hydrogen peroxide and a bleach activator compound as defined herein in the presence
2s of water, preferably with agitation. Typically the activator will be present at levels of
at least about 20 ppm in the water. The source of hydrogen peroxide will typically be
present at levels of at least S0 ppm.
CA 0220S412 1997-OS-15
WO 96/16155 PCT/US95/14687
By "effective amount" herein is meant an amount which is sllffirient~ under
whatever colllpaldli~e test conditions are employed, to enh~nce ~le~nin~ of a soiled
surface. Likewise, the term "catalytically effective arnount" refers to an amount
which is sufficient under whatever colllp~ /e test conditions are employed, to
s enh~nce cleAnin~ of a soiled surface.
All pel c~ gpc~ ratios and pl opol lions herein are by weight, unless otherwise
specified All doc~m~nt~ cited are, in relevant part, incorporated herein by rerelence.
DETAILED DESCRIPTION OF THE INVENTION
The present invention in~ludes bleach additives and bleaching compositions
0 colllpli~illg particularly selected bleach activators collectively referred to as
"pelru~lance-enh~nced bleach activators". The present invention further incllldes
novel bleach activator compounds which are a prer~lled sub-group of these
activators. The bleachin~ compositions herein, in general, cG~ ise a source of
bleach, typically a source of hydrogen peroxide, in addition to the activator
15 component. The bleach additive compositions, however, may or may not have a
hydrogen peroxide source built into the formulation. Whereas additive compositions
are generally used in conjunction with conv~ntion~l bleachcol-lA~ g dete,~:enls,especi~lly those form~ ted with sodium perborate or percarbonate, ble~chi~
compositions accolding to the invention are typically used as "stand-alone"
20 formulations delivering a full range of cl~nin~ and ble~hin~ effects.
As noted, p,~,ft.,~:d pe,r~l",~ce-enh~nced bleach activators herein con,p,ise
one or more RC(O)- and -L moieties. In general, more than one of each of these can
be present. Plcr~l~bly, one of each is present, and they are covalently col-ne.;le~i
Moieties RC(O) - In prere" ed bleach activators useful herein, R is
25 nol-~ gly illustrated by ele-;l,o,-~ali.~ely substih~ted phenyl s~?lected from the
group co~eietir~ of p-chlorophenyl, m-chlorophenyl, p-nitrophenyl, 3,5-
d;chlorophe.,yl, and 3,5-diniLro~)l e~yl, and mixtures thereo In yet other plerelled
embo~ 1 s, R is s~lected from alkylsulfonylphenyl, arylalkylsul~"~lph~;"~rl,
alkylsulfonyl naphthyl, arylalkylsulfonyl-naphthyl, and n~lul~s thereo Note that
30 when naphthyl is selecled lln~ubstihlted 1-naphthyl or sllbstihlted 1- or 2-ndphll,~l is
p,ert;llt;d. Other ~ ?l~s of plefe"cd bleach activators include those wl,er~. R is
a substihlted or wls.~ uted furan, and wherein R is s~ ..l;Ally free from chloro-
or nitro- substitu~nte
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
Leaving Groups - The L moieties in the pelr~-lllallce-.?nh~nced bleach
activators useful in this invention are preferably selected from the group consi~ g
of unsubstituted l~ct~m~, Substituted l~r,t~m~, substituted or lln~ubstituted 2-alkyl
4,5-dihy.lroi...;.1~701es, and Illi~ures thereo Particularly p-er~ d ~r , t~s of L
s are those selected from the group col1c~ of:
N~J~ and N~
Novel Pe,r~,l",ance-F.nh~n~ed Bleach Activator Compounds - In pr~rt;,ltid
10 novel bleach activator compounds of this invention, L is as intlic~ted supra and R is
selected from the group consisting of:
(I):
O
~_~A~--
A]
0=~=0
~,1
lS Whele;n a is independently 0 or 1, b is 0 or 1, A is sdected from 0 and NR2 wll~
R2 is H or methyl; when a is 0 or when a is 1 and A is 0, Rl is sdected from alkyl,
arylalkyl, alkoxy, aryloxy, alkylamino, and arylamino; when a is 1 and A is other than
o, R1 is s~lecled from alky! and arylalkyl; and
(II) furan or s~lbstituted furan, having the formula:
T~
whel~ T is selected from the group con~ ;ug of H, N02, Br, alkyl, and arylalkyl.In a highly plc;fell~d embodiment ofthe pelrullllance boosting bleach activator,L is prefelably sde~,led from the group co~ s of:
CA 02205412 1997-05-15
WO 96/1615S PCT/US95/14687
0~ 0
~) or N~
and R is s~lected from the group consisting of:
Rl~SJ~ ' Tl~ or
O=S=O O
S Rl
wlleleu1 Rl is selected from alkyl, arylalkyl, alkoxy, aryloxy, alkylamino, and aryl-
amino; and T is selected from the group con.~ ~I;ng of X Br, and NO2.
Compositions comprising these novel compounds are also inr.h~ded in the scope ofthis invention.
lo pK~ Rate and Perhydrolysis Criticalities - In accold~lce with the present
invention, there are provided ble?~hing compositions wherein the bleach activators
are required to respect critir,~lities of PKa and criticalities relating to rates of
perhydrolysis, hydrolysis and dia.;ylpelc,~de formation. Furthel~llole, p~.llydlulysis
~rr4;Ç~.r,~ is impolLa,ll in sp1ecl;np the bleach activator. All ofthese criticalities will be
15 better understood and appl ec;a1ed in light of the following disclosure.
~ a Value - The acids in which organic ch~ s have tra~lition~lly been
illt~e~led span a range, from the weakest acids to the strongest, of about 60 pKunits. Because no single solvent is suit~ble over such a wide range, est~blish~ of
c~..lprehens;~re scales of acidity n~c~ les the use of several di~ele.ll solvents.
20 Ideally, one might hope to construct a universal acidity scale by relating results
obL~ ed in dintre.lL solvent systems to each other. Primarily because solute-solvent
inlela~ ons affect acid-base equilibria diffently in dif~rell~ solvents, it has not proven
pos5ibl~ to est~hli~h such a scale.
Water is taken as the standard solvent for establishing an acidity scale. It is
25 convenient, has a high dielectric con~ and is effective at solvating ions.
CA 0220~412 1997-0~
WO 96/1615~ PCT/US95/14687
Equilibrium ac;~ities of a host of compounds (e.g., carboYylic acids and phenols)
have been de~e.~llined in water. Compilations of pK data may be found in Perrin, D.
D. "Dissociation Collsl~lts of Organic Bases in Aqueous Solution"; Bullclw~JILhs:
London, 1965 and Suppl~ment, 1973; Serjeant, E. P.; Dempsey, B. "Ionisation
5 ConsLanls of Organic Acids in Aqueous Solution"; 2nd ed., Pclgan~llon Press:
Oxford, 1979. EA~ al methods for detellni~ g PKa values are deswil,ed in
the original papers. The PKa values that fall between 2 and 10 can be used with a
great deal of confidçnce; however, the further removed values are from this range,
the greater the degree of skepticism with which they must be viewed.
For acids too strong to be invçstig~ted in water solution, more acidic media
such as acetic acid or miYtures of water with perchloric or sulfuric acid are
commonly employed; for acids too weak to be ~Y~mined in water, solvents such as
liquid ~mmo~ cyclohexylamine and dimethylsulfoYide have been used. The
~mmPtt Ho acidity function has allowed the aqueous acidity scale, which has a
15 practical PKa range of about ~12, to be eYt~nded into the region of negative PKa
values by about the same range. The use of H_ acidity functione that employ strong
bases and cosolvents has similarly eytçnrled the range upward by about 12 pKa units.
The present invention involves the use of leaving groups the conjugate acids of
which are considered to be weak; they possess aqueous pKa values greater than
20 about 13. To establish only that a given compound has an aqueous pKa above about
13 is strai~hlrol~ald. As noted above, values much above this are difficult to
c~ule with confidense without lesollillg to the use of an acidity fi.nctio~ The
Illea~lt;lncn~ of the acidity of weak acids using the H_ method, which has the
advantage of an aqueous standard state, is suitable for dclclllli~ g if the coniu~te
2s acid, HL, of leaving group, L, has an aqueous pKa of greater than about 13 to less
than about 17. Hovever, it is restricted in that (1) it rc.~ cs extrapolation across
varying solvent media and (2) errors made in delc,..l.ining inrlic~tor pKa values are
re. For these and other reasons, Bordwell and co-workers have developed a
scale of acidity in di~ foxide (DMSO). This solvent has the ad~r~.lag.i of a
30 relatively high diele~,LIic co~c~ 1 (E = 47); ions are Ih~rcrole ~icso~istpd so that
p-oblenls of dirrtlcl"ial ion pairing are reduced. ~Itho~lgh the results are rcrell~,d to
a ~land~d state in DMSO instead of in water, a link with the aqueous PKa scale has
been made. When aci~litips n.e~culed in water or on a water-based scale are
co.ll~,~cd with those ll.eas.llcd in DMSO, acids whose conjugate bases have their
CA 02205412 1997-05-15
PCT/US95/14687
WO 96/16155
11
charge localized are stronger acids in water; acids whose conjugate bases have their
charge delocalized over a large area are usually of co,llpa-~ble strength. Bordwell
details his findings in a 1988 article (Acc. C~em. Res. 1988, 21, 456~63).
Procedures for measurement of pKa in DMSO are found in papers l~rtl~nced
5 therein.
Definitions of kH kp. and k2 - In the eA~ ssions given below, the choice of
whether to use the concentration of a nucleophile or of its anion in the rate equation
was made as a matter of conv~nienre One skilled in the art will realize that
measurement of solution pH provides a convenient means of directly measuring the0 concel,L,a~ion of hydroxide ions present. One skilled in the art will further recogr~ize
that use of the total concentrations of hydrogen peroxide and peracid provide the
most convenient means to determine the rate con~a"ts kp and kD.
The terms, such as RC(O)L, used in the following definitions and in the
conditions for the dete~ na~ion of kH, kp and kD, are illustrative of a general bleach
15 activator structure and are not limiting to any specific bleach activator structure
herein.
Definition of kH
RC(O)L + HO- ~ RC(O)O- + HL
The rate of the reaction shown above is given by
20 Rate = I~H~RC(O)L][HO ]
The rate constant for hydrolysis of bleach activator (J~H) is the second order rate
con~ l for the bimolecular reaction between bleach activator and hydroxide anionas deterrnined under the conditions specified below.
Definition of kp
25 RC(O)L + H22 ~ RC()2H + HL
The rate of the reaction shown above is given by
Rate = kp[RC(O)L~[H202]T
where [H202]T l~;~I'tSenLS the total cQncçntration of hydrogen peroxide and is
equal to ~H2o2] + [H2 ~
CA 0220S412 1997-OS-lS
WO 96/16155 PCT/US95/14687
12
The rate constant for perhydrolysis of bleach activator (kp) is the second order rate
constant for the bimolecular reaction between bleach activator and hydrogen
peroxide as determined under the conditions specified below.
Definition of kD
RC(O)L + RC(0)02H ~ RC(0)02C(0)R + HL
The rate of the reaction shown above is given by
Rate = kD~[RC(O)L][RC(0)02HlT
where [RC(0)02H]T r eprese.lls the total concentration of peracid and is equal to
[RC(0)02Hl + [RC(0)02 ]-
lo The rate constant for the formation of a diacylperoxide from the bleach activator
(1~), the second order rate constant for the bimolecular reaction between bleachactivator and peracid anion, is c~lcul~ted from the above defined kD~. The valuefor kD~ is determined under the conditions specified below.
Conditions for the Dete...,hlalion of Rate Con~la.~ls
Hydrolysis - A set of cA~IilllellLs is comrleted to measure the rate of
hydrolysis of a bleach activator RC(O)L in aqueous solution at total ionic ~ n~ Ih
of lM as adjusted by addition of NaCI. The te,..p~ ure is ...A;~ d at 35.0 i
0.1 C and the solution is buffered with NaHC03 + Na2C03. A solution of the
activator ([RC(O)L] = 0.5 m~ is reacted with valying conc~ lions of NaOH
20 under stopped-flow co~ n~ and the rate of reaction is nlolliloltd optically.
Reactions are run under pseudo first-order contiitione to dt;ltlllfi"e the bimoleclll~r
rate co~ for hydrolysis of bleach activator (k~). Each kinetic run is l~pedled
at least five times with about eight dirrelen~ co~ce~ alions of hydroxide anions.
All kinetic traces give s~tief~ctQrv fits to a first-order kinetic rate law and a plot of
25 the observed first-order rate con~ versus col-c~ alion of hydroxide anion is
linear over the region investig~ted The slope of this line is the derived secondorder rate con~l~ll kH
Pe~hyd,ulysis - A set of experiments is comrleted to measure the rate of
pelllydlolysis of a bleach activator RC(O)L in aqueous solution at pH = 10.0 with
30 cor.~ ionic sl,~.,glh of lM as adjusted by ~ltlitioll of NaCI. The telllpc~al~lre is
ed at 35.0 _ 0.1 C and the solution is buffered with NaHC03 + Na2C03.
A solution of the activator ([RC(O)L] = 0.5 mM) is reacted with varying
~ = =
CA 0220~412 1997-o~
WO 96/16155 PCT/US95/14687
13
concçntrations of sodium perborate under stopped-flow conditions and the rate ofreaction is monitored optically. Reactions are run under pseudo first-order
conditions in order to determine the bimolecular rate constant for perhydrolysis of
bleach activator (kp). Each kinetic run is repeated at least five times with about
5 eight din'crcnl conce~ ions of sodium perborate. All kinetic traces give
s~tisf~ctory fits to a first-order kinetic rate law and a plot of the observed first-
order rate constant versus total concentration of hydrogen peroxide is linear over
the region investigrtte~ The slope of this line is the derived second order ratecoAC~n~ kp. One skilled in the art recognizes that this rate cQn~ iS distinct
o from, but related to, the second order rate con~l~..l for the reaction of a bleach
activator with the anion of hydrogen peroxide (k~7UC). The relationship of these rate col~L~.~ts is given by the following equation:
knUC = kp {(Ka + [H+~)lKa}
where Ka is the acid dissociation constant for hydrogen peroxide.
IS Formation of diacylperoxide - A set of experiments is co........ l-leled to measure
the rate of formation of a diacylperoxide RC(0)02C(O)R from a bleach activator
RC(O)L in aqueous solution at pH = 10.0 with coh~lant ionic strength of lM as
adjusted by addition of NaCI. The temperature is m~int~ined at 35.0 + 0.1 C andthe solution is buffered with NaHC03 + Na2C03. A solution of the a~ ,alor
([RC(O)I,] = 0.5 mM) is reacted with varying concentrations of peracid under
stopped-flow con~lition-c and the rate of reaction is monitored optically. Re~ctiQnc
are run under pseudo first-order conditiortc in order to dclclllline the bimolecul~r
rate cor.~n~ kD~. Each kinetic run is repeated at least five times with about eight
di~crcu~l conce.lllalions of peracid anion. All kinetic traces give s~tticf~ctQry fits to
2s a first-order kinetic rate law and a plot of the observed first-order rate con~
versus total conr~ ion of peracid is linear over the region im~c~ ed The
s10pe of this line is the derived second order rate con~L~Il kD~. The bim~le.,ul~r
rate cor.... ......~ for the formation of a diacylperoxide from peracid anion (kD) is
ç~iç~ ted accol dillg to
kD = kD~ {(Ka + [Ht])/Ka}
where Ka is the acid ~iCsoci~tiQn Co~ l for the peracid RC(0)02H. One skilled
in the art will realize that the PKa values for peracids fall into a rather narrow range
CA 0220~412 1997-o~
WO 96/16155 14 PCT/US95/14687
from about 7 to about 8.5 and that at pH = 10.0 when Ka 2 about 10-8, {(Ka +
[H+])/Ka} _ 1 and kD - kD'
Test for Low pH Perhydrolysis Efficiency - This method is applicable as a test for
s~iree~ g any bleach activators RC(O)L (not inten-ling to be limiting of any speciffc
s pe.r~""~allce F~.~h~l~ced bleach activator structure herein) by collrl""d~ion of the
formation of peracid analyte RC(0)02H. The minimllm standard for low pH
perhydrolysis efficie~cy (LPE) is a coefficient, as defined below 2 0.15 within 10
minllteS when tested under the conditions specified below.
Test Protocol - Distilled, deionized water (495 mL; ~ ted to pH 7.5 with
lo NaH2P04 and Na2HP04) is added to a 1000 mL beaker and heated to 40 ~ 1 C.
Three hundred seventy-five (375) mg of 30% conce"l,~tion hydrogen peroxide is
added to the beaker and the mixture is stirred for two minutes before a 5 mL solution
cont~ining 100 mg of activator (predissolved in 5 mL of an organic solvent (e.g.meth~nol or dimethylru.,..~ de)) is added. The initial data point is taken 1 minute
15 thereafter. A second sample is removed at 10 minlltes Sample aliquots (2 mL) are
eY~mined via analytical HPLC for the q~ e dt;~e""i"dlion of peracid
RC()2H
Sample aliquots are individually mixed with 2 mL of a pre-chilled 5 C
sollltion of acc~o~ .ile/acetic acid (86/14) and placed in te"")e,~ re controlled 5
20 C ~ltos~mpler for subsequent injection onto the HPLC column.
High p~,ro~,,dllcc liquid cl,ro"lalography of the a~.thrntic peracid under a
given set of conditions est~blishes the characteristic retention time (tR) for the
analyte. Conditions for the ch,u"~dlography will vary depending on the peracid of
interest and should be chosen so as to allow b~çline separation of the peracid from
2s other analytes. A standard calibration curve (peak area vs. conce~ alion) is
constructed using the peracid of interest. The analyte peak area of the 10 minute
sarnple from the above desc,ibed test is thereby converted to ppm peracid
geh~aled for d~;te""i"àlion of the quantity LPE. A bleach activator is conQ;dered
acceptable when a value of the low pH perhydrolysis efficienry corfficient LPE =30 ~(ppm of peracid g~llwaled)/(theoretical ppm peracid)] 2 0.15 is achieved within
ten rnin--t~s under the specified test collrlition~
To note, by co"~ison with 4,5-saturated cyclic amidine embodimrnt~ of the
instant bleach activators, known closely related chem;~l compounds wLe;lein the 4,5
position is ull~alulaled have surprisingly greater rates of hydrolysis. Specifir~lly,
CA 0220~412 1997-0~
WO 96/16155 PCT/US9~/14687
acetyl imidazole has kH greater than 10.0 M-l s-1: accordingly this invention does
not encompass imidazole as a leaving group.
Bleaching Compositions - Effective bleach-additives herein may comprise the
bleach activators of this invention without a hydrogen peroxide source, but
pelerc~ably include deLelge,ll surf~ct~nt~ and one or more members selected from the
group cor~ g of low-foaming automatic dishwashing surf~ct~nte ethoxylated
noniQnic surf~ct~nts, bleach stable thickeners, transition-metal r.h~ nt~ builders,
flourescent whitening agents (also known as bri~hteners), and buffering agents.
However, for ble~ching compositions, the bleach activators herein are not p~crcl~bly
0 employed alone but in combination with a source of hydrogen peroxide, as disclosed
hereinafter. Levels of the bleach activators herein may vary widely, e.g., from about
0.1% to about 90%, by weight, of composition, although lower levels, e.g., from
about 0.1% to about 30% are more typically used.
Source of hydrogen peroxide - A source of hydrogen peroxide herein is any
15 convenient compound or mixture which under cor ~ ~mer use conditions provides an
effective amount of hydrogen peroxide. Levels may vary widely and are typically
from about 0.5% to about 70%, more typically from about 0.5% to about 25%, by
weight of the bleaching compositions herein.
The source of hydrogen peroxide used herein can be any convenient source,
20 inclu-ling hydrogen peroxide itsel For e,.~lll},lc, perborate, e.g., sodium pclbo~ate
(any hydrate but plcrclably the mono- or tetra-hydrate), sodium calbohale
pc,uAylly.llale or equivalent percarbonate salts, sodium pyrophosph~te
pcro~yhydrate, urea peroxyhydrate, or sodium peroxide can be used herein.
Mixtures of any convenient hydrogen peroxide sources can also be used.
A ~ fe.lcd pe;c~l,ollate bleach co~ ,ises dry particles having an avcl~c
particle size in the range from about 500 Inic~olllclel~ to about 1,000 I,liclo,,,cters,
not more than about 10% by weight of said particles being smaller than about 200ll~clolllcLc,~ and not more than about 10% by weight of said particles being larger
than about 1,2~0 miclo,llclcl~. Optionally, the percarbonate can be coated with
30 silicate, borate or water-soluble surf~ct~nts PclcdllJonâte is available from various
comrnercial sources such as FMC, Solvay and Tokai Denka.
Fully-fo,..~ ted laundry and automatic dishwashing co"lposilions typically
will also co,llplise other adjunct ingredients to irnprove or modify p~.ro""ancc.
CA 02205412 1997-05-15
WO 96/16155 PCT/US95114687
16
Typical, non-limiting examples of such ingredients are disclosed hereinafter for the
convenience of the formulator.
Adjunct Ingredients
Bleach catalysts - If desired, the bleaches can be catalyzed by means of a
s m~n~nece compound_Such compounds are well known in the art and u~.c!ude, for
example, the m~nese-based catalysts dicnlosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub.Nos. 549,271Al, 549,272Al, 544,440A2, and 544,490Al; Prere,lcd examples of
these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-
10 (PF6)2, ~III2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)2,
MnIV4(u-0)6(1,4,7-triazacyclononane)4(C104)4,
MnIII~MnIV4-(u-O) 1 (u-OAc)2-(1,4,7-trimethyl- 1,4,7-triazacyclo-nonane)2-
(CIO4)3, ~IV~(1,4,7-trimethyl-1,4,7-triazacyclo-nonane)-(OCH3)3(PF6), and
mixtures thereo Other metal-based bleach catalysts include those r~icclosed in U.S.
5 Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of m~ng~nese with various
complex ligands to enh~nce ble~rhin~ is also reported in the following United States
Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147;
5,153,161; and 5,227,084.
Said ~ p,S~l~F5e can be plecG.,.~ PYed with ethylened;;~n;..P~ uctin~te or
20 s~,paralely added, for eY~mple ac a sulfate salt, with ethyl~ .e ~ P~IisucGin~te (See
U.S. Application Ser. No. 08/210,186, filed March 17, 1994.) Other p,efc,~.,d
tr~ncition metals in said transition-metal-co,~ bleach catalysts include iron or
copper.
Remarkably, prefcn~cd embodimPntc of the present invention in which the
2s wash pH is in the range from about 6.5 to about 9.5 and there is present one of the
above-indic~ted sele~led pc~ru""al~ce-enh~nced bleach activators in coll,l)inalion
with one of the above-indiG~d bleach catalysts, secure a particularly superior
b'~1~hing effect as con,p~d with otherwise ident~ co"lpo~ ions in which
conv~ntion~l bleach activators such as TAED (see hele;,~elow) are used in place of
30 the l)e.ru""ance-enh~nced bleach activator.
As a practical matter, and not by way of limit~tion, the blo~^hin~
compositions and processes herein can be adjusted to provide on the order of at least
one part per ten million of the active bleach catalyst species in the a~ueo~s washing
liquor, and will prefe,ably provide from about 0.1 ppm to about 700 ppm, more
CA 0220~412 1997-0~
WO 96/16155 PCT/US9S/14687
17
preferably from about 1 ppm to about 50 ppm, of the catalyst species in the laundry
liquor.
Conventional Bleach Activators - "Conventional bleach activators" herein are
any bleach activators which do not respect the above-idçntified provisions given in
- 5 connection with the pe,rol",ance-boosting bleach activators. Numerousconventional bleach activators are known and are optionally inclllded in the instant
ble~ching compositions. Various nonlimiting examples of such activators are
disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S.Patent 4,412,934. The nonanoyloxyben_ene sulfonate (NOBS) and tel,~act;Lyl
0 ethylenedi~mine (TAED) activators are typical, and mixtures thereof can also be
used. See also U.S. 4,634,551 for other typical conventional bleach activators.
Known amido-derived bleach activators are those of the formulae:
R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L wherein Rl is an alkyl group
co~ ;.,g from about 6 to about 12 carbon atoms, R2 is an alkylene cor~ g from
5 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl co~ ;ng from about 1
to about 10 carbon atoms, and L is any suitable leaving group. Further illustration of
optional, conventional bleach activators of the above formulae include (6-
oct~n~mido-caproyl)oxybçn7~ne~--1fonate, (6-non~n~midocaproyl)o~yl,~n~ P~
fonate, (6-dec~n~m;~o-caproyl)oxyben7~nes-.lfon~te and mixtures thereof as
described in U.S. Patent 4,634,551. Another class of conv~ntion~l bleach aclivalo,s
comprises the b.~l-,o,~;.,;..-type activators disclosed by Hodge et al in U.S. Patent
4,966,723, issued October 30, 1990. Still another class of convention~l bleach
activators inclllde5 those acyl lactam activators which do not provide the benefits and
criticalities described herein. Examples of optional lactam activators include octanoyl
2s caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprol~ct~m, dec~1oyl
caprol~ct~m u~-decçnoyl caprol~r.t~m, octanoyl valerol~ct~m decanoyl valero~ m
Im~3ecçnoyl valerol~ct~m, nonanoyl valerol~ct~m, 3,5,5-L~ Lh~ ,AanOyl
valerolactam and mixtures thereo
Ble~çhing agents other than hydrogen peroxide sources are also known in the
30 art and can be utilized herein as adjunct hlgl~die.lLs. One type of non-oxygen
ble~ching agent of particular interest incl~des photoactivated ble~ch;~.g agents such
as the sulrollated zinc and/or al-.minnm phthalocyanines. See U.S. Patent 4,033,718,
issued July 5, 1977 to Holco",be et al. If used, d~;LelgenL compositions will typically
=
CA 0220~412 1997-0~
WO 96/16155 PCT/US9S/14687
18
contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially
sulfon~ted zinc phthalocyanine.
Organic Peroxides. especially Diacyl Peroxides - are extensively illustrated in
Kirk Othmer, Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons,
1982 at pages 27-90 and esper,i~lly at pages 63-72, all incorporated herein by
reference. Suit~hle organic peroxides, especially diacyl peroxides, are further
illustrated in "Initiators for Polymer Production", Akzo Chemicals Inc., ProductCatalog, Bulletin No. 88-57, incorporated by reference. P~c:felled diacyl peroxides
herein whether in pure or form~ ted form for granule, powder or tablet forms of the
0 bleaçhing compositions con~titllte solids at 25C, e.g., CADETe~) BPO 78 powder
form of dibenzoyl peroxide, from Akzo. Highly pic:felled organic peroxides,
particularly the diacyl peroxides, for such bleaching compositions have melting points
above 40C, preferably above 50C. Additionally, p~relled are the organic
peroxides with SADT's (as defined in the foregoing Akzo publication) of 35C or
15 higher, more prerel~bly 70C or higher. Nonlimiting eAalllples of diacyl peroxides
useful herein include dibenzoyl peroxide, lauroyl peroxide, and dicumyl peroxide.
Dibenzoyl peroxide is plere;lled. In some in~t~nr,es, diacyl peroxides are available in
the trade which contain oily s~1bst~nces such as dioctyl phth~l~te In general,
particularly for automatic dishwashing applications, it is pl~f~llt;d to use diacyl
20 peroxides which are sub~ ially free from oily phth~l~tes since these can form smears on dishes and glassware.
QuaL~:ll.a.y S~lbstituted Bleach Activators - The present compositions can
optionally further comprise convention~l known qualtll.aly s~lbstituted bleach
activators (QSBA). QSBA's are further illustrated in U.S. 4,539,130, Sept. 3, 1985
2s and U.S. Pat. No. 4,283,301. British Pat. 1,382,594, I,.lt.li~l.ed Feb. 5, 1975,
~icrloses a class of QSBA's optionally suitable for use herein. U.S. 4,818,426 issued
Apr. 4., 1989 di~rloses another class of QSBA's. Also see U.S. 5,093,022 issued
March 3, 1992 and U.S. 4,904,406, issued Feb. 27, 1990. ~d~lition~lly~ QSBA's are
des-libed in EP 552,812 A1 published July 28, 1993, and in EP 540,090 A2,
30 pub!i~hed May 5, 1993.
Detersive Surfactants --Surf~nt~ are useful herein for their usual ~le~ g
power and may be jnclufled in Illert:lled embodiments of the instant compositions at
the usual detergent-useful levels. Such co~.ll.;..Al;on~ are better than the sulr~
CA 0220~412 1997-o~
WO 96/16155 PCT/US95/14687
19
free counterparts in terrns of overall rle~ning and bleaching pe.ro,...allce and are
possibly synergistic.
Nonlimiting examples of surf~ct~ntc useful herein include the conventio~
Cll Clg alkylbenzene sulfonates ("LAS") and primary, branched-chain and random
- 5 Clo-C20 alkyl sulfates ("AS"), the Clo-Clg secondary (2,3) alkyl sulfates of the
formula CH3(CH2)X(CHOSO3-M+)CH3 and CH3(CH2)y(CHOSO3~M ) CH2CH3
where x and (y + 1) are integers of at least about 7, preferably at least about 9, and
M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl
sulfate, the Clo-Clg alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy
0 sulfates), Clo-Clg alkyl alkoxy carboxylates (especially the EO 1-5
ethoAy.;~.l,oAylates), the Clo-Clg glycerol ethers, the Clo-Clg alkyl polyglycosides
and their co..t~ onding s~lf~ted polyglycosides, and C12-Clg alpha-sulfonated fatty
acid esters. If desired, the conventional nonionic and amphoteric surf~rt~ntc such as
the C12-Clg alkyl ethoxylates ("AE") inr,lu-ling the so-called narrow peaked alkyl
5 ethoxylates and C6-C12 alkyl phenol alkoxylates (espec~ y ethoxylates and mixed
ethoxylate/propoxylates), C12-Clg betaines and sulfobetaines ('~sult~inesll)7 C10-cl8
amine oxides, and the like, can also be incl~ded in the overall comro~citions The
C1o-C1g N-alkyl polyhydroxy fatty acid arnides can also be used. Typical c A~.. r!es
include the C12-Clg N-methylglllc~m;d~s See WO 9,206,154. Other sugar-derived
20 surf~ct~nts include the N-alkoxy polyhydroAy fatty acid amides, such as Clo-Clg N-
(3-methoxypropyl) gl~ç~m;~e The N-propyl through N-hexyl C12-C1g glucamides
can be used for low su~lcing C lo-C20 convention~l soaps may also be used. If high
sudsing is desired, the b.~1ched-chain Clo-C16 soaps may be used. Mi~Atures of
anionic and nonionic surf~r,t~ntc are especially useful. ~-ltom~tic dishwashing
2s co..,posilions typically employ low sudsing surf~ct~ntc, such as the miAed
ethylelle~.A~ ro~le..~,~.~ nonion;cs Other convention~l useful surfact~ntc are listed
in s~anddrd texts.
Builders - Delt,~,e"l builders can optionally be inr,lllded in the compositions
herein to assist in controlling mineral har.llless. Inol ~anic as well as organic builders
30 can be used. Builders are typically used in ~utQm~tiC disl~w~Lsl"llg and fabric
laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composilion and its desired physical form. When present, the compositions will
typically comprise at least about 1% builder. High pe,~""ance compositions
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
typically comprise ~om about 10% to about 80%, more typically from about 15% to
about 50% by weight, of the detergent builder. Lower or higher levels of builder,
however, are not excluded.
Inorganic or P-cont~ining de~e,genl builders include, but are not limited to,
the alkali metal, amrnonium and ~Ik~nol~mmonium salts of polyphosphates
(exeml)lified by the tripolyphosph~tçc~ pyrophosphates, and glassy polymeric meta-
phosphates), phosphonates, phytic acid, silicates, carbonates (inclu~ing bica,l.Onales
and sesquicarbonates), sull-h~te~ and ~lllminocilic~tpc However, non-phnsph~te
builders are required in some locales. Importantly, the compositions herein ~filnction
0 surprisingly well even in the presence of the so-called "weak" builders (as col"~,~cd
with phosphates) such as citrate, or in the so-called "underbuilt" sit l~tion that may
occur with zeolite or layered silicate builders. See U.S. Pat. 4,605,509 for examples
of p-cfelled ~luminosilicates.
Examples of silicate builders are the alkali metal 5ilic~tPc particularly those
having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1 and layered si~ tes~ such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987
to H. P. Rieck. NaSKS-6~g) is a crystalline layered silicate ,,,~I~cLed by Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6
silicate builder does not contain al~.min~m NaSKS-6 is the ~-Na2SiOs morphology
20 form of layered silicate and can be p,epared by methods such as those des~,,il)ed in
Gerrnan DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly pref~.lcd layered
silicate for use herein, but other such layered silicates, such as those having the
general formula NaMSixO2x+pyH2O wherein M is sodium or hydrogen, x is a
number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, pl~fclably 0 can
2s be used herein. Various other layered silic~tes from Hoechst include NaSKS-5,NaSKS-7 and NaSKS-l l, as the a-, ,B- and y- forms. Other Cilic2tp~s may also beuseful, such as for ~"~a""i)lc ma~nesil~m silicate, which can serve as a .;l;~ g agent
in gl~wlar forrnulations, as a st~hili7in~ agent for oxygen b'ea~h~c, and as a
coln~on~ of suds control systems.
Sili~tPs useful in ~utom~tic dishwashing (ADD) app~ tionc include granular
hydrous 2-ratio silic~tes such as BRITES~ H20 from PQ Corp., and the
collllllollly sourced BRITESIL~) H24 though liquid grades of various silic~te~ can be
used when the ADD co",~os;lion has liquid forrn. Within safe limits, sodium
CA 0220~412 1997-0~
WO 96/16155 PCT/US95/14687
21
metasilicate or sodium hydroxide alone or in combination with other silicates may be
used in an ADD context to boost wash pH to a desired level.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published on
s November lS, 1973. Various grades and types of sodium carbonate and sodium
sesquicarbonate may be used, certain of which are particularly useful as carriers for
other ingredients, especially detersive surf~ct~nt~
~ Inminosilir.~te builders are useful in the present invention. Alu~".l.osilicate
builders are of great importance in most currently Illall~eled heavy duty granular
o d~le.~,cl" compositions, and can also be a significant builder ingredi~ in liquid
de~er~tnt formulations. Aluminosilicate builders include those having the empirical
formula: [Mz(zA102)y] xH20 wherein z and y are integers of at least 6, the molarratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15
to about 264.
1S Useful ahlminosilicate ion PYch~n~e materials are col"",e.-,;ally availab!e.
These alnmino~ilir,ates can be crystalline or amorphous in structure and can be
naturally-occurring ~lllminnsilir~tpe or synthetiç~lly derived. A method for
producing aluminosilic~te ion PYçh~n~e materials is ~ closed in U.S. Patent
3,985,669, Krumrnel, et al, issued October 12, 1976. Prerelled synthetic crystalline
~ minosilic~te ion eYch~n~e materials useful herein are available under the
de~iEn~tions Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially
plc;rt:lled embodiment, the crystalline alumino.~ te ion ~ ge material has the
formula: Nal2[(AIO2)12(SiO2)12]-XH2O wherein x is from about 20 to about 30,
~speri~lly about 27. This material is known as Zeolite A. Del,~l,aled zeolites (x = O
2s - 10) may also be used herein. Plefel~bly, the ~luminosilic~te has a particle size of
about 0.1-10 microns in ~i~met~r. As with other builders such as call,onales, it may
be desirable to use zeolites in any physical or morpholc~ 1 form adapted to
pfolllole surfactant carrier function, and appropll~le particle sizes may be freely
selecle~ by the formulator.
Organic delelgellL builders suitable for the purposes of the present invention
inrlude, but are not restricted to, a wide variety of polycall,u~late compounds. As
- used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate
groups, preferably at least 3 carboxylates. Polyc~l,.~late builder can generally be
added to the composition in acid form, but can also be added in the form of a
CA 0220~412 1997-0~
WO 96/161S5 PCTIUS95/14687
22
neutralized salt or "overbased". When utilized in salt forrn, alkali metals, such as
sodium, pot~C.cillm and lithium, or alkanolammonium salts are pltft~ d.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders encomr~cce
s the ether polycarboxylates, in~lntling oxytlicuc~.in~te~ as diccl(?sed in Berg, U.S
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include
cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
10 Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypoly-ialbo~lates,
copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxyrnethyloxysuc~inic acid, the
various alkali metal, ammonium and substituted ammonium salts of polyacetic acids
5 such as ethylenedii.,..;~letetraacetic acid and nitrilotriacetic acid, as well as
polycarboxylates such as mellitic acid, succinic acid, oxydicuccinic acid, polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxyrnethyloxysuc~inic acid, and soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
20 salt), are polycarboxylate builders of particular importance for heavy duty laundry
dete,~;e..l forrn-~l~tiQ~c due to their availability from renewable resoul~ies and their
biodegradability. Citrates can also be used in cor..lJi~ ;Qn with zeolite and/or layered
silicate builders. Oxyriicllc~in~tes are also especially useful in such compositions and
CGI~ iQnc
2s Also suitable in the dtLel~5en~ compositions of the present invention are the
3,3-dicalbuA~4-oxa-1,6-h. ~ etlio~tçlc and the related compounds iicclosed in U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful sucçin:c acid builders
include the Cs-C20 alkyl and alkenyl sucçinic acids and salts thereo A particularly
plc;fell~,d compound of this type is dodecenylc~1ccinic acid. Specific eY~mples of
sucçin~te builders include: laurylcuccin~tç~ myristyl.cuccin~tç, palmityl.cucçin~tç 2-
dodecenylcuc~in~te (plert;..~d), 2-pent~decenyl.~ucçin~te, and the like.
Laurylcucçin~tPs are the p.ert;..ed builders of this group, and are described inEuropea~1 Patent Applicalion 86200690.5/0,200,263, published November 5, 1986.
-
CA 02205412 1997-05-15
WO 96/1615S PCT/US95114687
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Cn~tchfield èt al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued
March 7, 1967. See also U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be h~colpolaled
- 5 into the compositions alone, or in combination with the aforesaid builders, especially
citrate and/or the succin~te builders, to provide additional builder activity. Such use
of fatty acids will generally result in a ~imimltion of su~lcin~ which should be taken
into account by the formulator.
In situations where phosphorus-based builders can be used, and espec~ y in
the formulation of bars used for hand-laundering operations, the various alkali metal
phos~,hales such as the well-known sodium tripolyphosph~t~oc sodium pyrophosphate
and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-
hydroxy-l,l-diphosphonate and other known phosphonates (see, for ~ .lc, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be
used.
Chel~tin~ Agents - The compositions herein may also optionally contain one
or more iron and/or ~ g~nese chel~tin~ agents, such as diethylen~l-;amil.el,cllla
acetic acid (I)TPA). More generally, çhel~ting agents suitable for use herein can be
s~lected from the group con~is~ g of aminoç~rboxylates, a.. i..ophosl.hon~$,
20 polyfilnctiQn~lly-substituted aromatic çhel~tin~ agents and mixtures thereo Without
;. lel~ g to be bound by theory, it is believed that the benefit of these materials is
due in part to their exceptional ability to remove iron and .~ nese ions from
washing sol~ltionc by formation of soluble chPl~t~s; other benefits include inorganic
film or scale prevention. Other suitable ~.h~ ting agents for use herein are the2s co.... -c;al DEQUEST~ series, and cl-el~ c from ~ol~c~.. lo, DuPont, and Nalco,
Inc.
,~minoc~rboxylates useful as optional c~ tii~ agents include
ethylGne~ et~ cet~c~ N-hy.l~o~eLllylethyle--cd;~.;ne~ c~ c,
nitrilotri~cet~tes, ethyle~ .e tel. ~p~ op- ionates,
30 triethylenet~ mil~Fk~~cet~t~c~ diethyleneLli&~llinc-ppnt~cet~tec and
eth~noldigly-,ines, alkali metal, a....--o..: -m, and s~lbstitllted ~m.~ol~ m salts therein
and ~ u.~s therein.
A,llillophos~,honates are also suitable for use as chel~l;..g agents in the
compositions of the invention when at least low levels of total phosphorus are
CA 0220~412 1997-0~
WO 96/16155 PCT/US95114687
permitted in detergent compositions, and include ethylenetli~minf tetrakis
(methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl
or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic r~hel~tin~ agents are also useful in the
compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et
al. Plc;re.,ed compounds ofthis type in acid form are dihydro~disulfoben7Pnr,s such
as 1,2-dihydroxy-3,5-disulfobel~tne.
A highly p.~;r~..ed biodegradable chelator for use herein is ethylene.~ e
rlic~cçin~te ("EDDS"), especially (but not limited to) the [S,S] isomer as des.;.il.ed in
U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The trisodium
salt is p-~rt:--ed though other forms, such as m~gnrcillm salts, may also be useful.
If utilized, especi~lly in ADD compositions, these çhrl~tir~ agents or
transition-metal-selective sequestrants will preferably comprise from about 0.001%
to about 10%, more preferably from about 0.05% to about 1% by weight of the
bleaching compositions herein.
Enzymes - Enzymes can be inrl.~ded in the form~ tionc herein for a wide
variety of fabric laundering or other rle~nin~ purposes, inclll-lin~ removal of protein-
based, carbohydrate-based, or triglyceride-based stains, for f. S~ e, and for the
prevention of refugee dye transfer, and for fabric restoration. The enzymes to be
incorporated include proteases, amylases, lipases, celllll~cçc and peroxi~l~sçe, as well
as ll~ ul~s thereo Other types of enzymes may also be inrhlde~ They may be of
any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
However, their choice is governed by several factors such as pH-activity and/or
stability optima, thermostability, stability versus active dete.gf.,ls, builders, etc.. In
2s this respect bacterial or fungal enzymes are pre~el . ~;d, such as bacterial amylases and
prote~ct s, and fungal cr~ cre
Enzymes are normally inco.~,or~ed at levels sllfficient to provide up to about
S mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyrne per
grarn of the composition. Stated otherwise, the compositions herein will typically
CollllJIiSe from about 0.001% to about 5%, preferably 0.01~/o-1% by weight of a
CG--...-~-Cial enzyme p-c:pa-alion. Protease enzymes are usually present in suchco....~.e.~,ial prepa-~lions at levels sllffiriPnt to provide from 0.005 to 0.1 Anson units
(AU) of activity per gram of composition.
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. sub~ilis and B. Iicheniformis. Another suitable protease is
obtained from a strain of Racil~u~, having maximum activity throughout the pH range
of 8-12, developed and sold by Novo Industries AtS as ESPERASE~. The
- s ~lepa,~lion of this enzyme and analogous enzymes is described in British Patent
Specification No. 1,243,784 of Novo. Proteolytic tl~yl~les suitable for removingprotein-based stains that are commercially available include those sold under the
tr~Pn~mçs ALCALASE(~) and SAVINASE(g) by Novo Industries AtS (De.ll..~)
and MAXATASE~) by International Bio-Synthetics Inc. (The Netherlands). Other
0 proteases include Protease A (see European Patent Application 130,756, published
January 9, 1985) and Protease B (see European Patent Application Serial No.
87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et
al, published January 9, 1985).
An especially p.ere..ed protease, r~re..ed to as "Protease D" is a c~l,orlyl
15 hydrolase variant having an amino acid sequence not found in nature, which isderived from a precursor carbonyl hydrolase by substit~ltin~ a di~renl amino acid for
a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent
to position +76 in cGrnbi..a~ion with one or more amino acid residue positions
equivalent to those sele~ed from the group co~ ting of +99, +101, +103, +107 and20 +123 in Bacillus amyloliquefaciens subtilisin as desclil,ed in the patent applir~tio~
of A. Baeck, C.K. Ghosh, P.P. Greycar, R.R. Bott and L.J. Wilson, entitled
"PloLease-CG..~ g Cleaning Compositions" having U.S. Serial No. 08tl36,797
(P&G Case 5040), and "Bleaching Compositions Co.,lpt;~ing ~ro~se Enzymes"
having U.S. Serial No. 08/136,626.
2s Amylases include, for eY~mrl~ a-amylases desvlil,ed in British Patent
Spe~ ;oll No. 1,296,839 (Novo), RAPIDASE~, Illlel..~l;o~ sio-Synth~tirc
Inc. and TERMAMYL~, Novo Industries.
Cçll~ ces usable in the present invention include both ba.;l~,.ial or fungal
c~llul~ces Preferably, they will have a pH Opti~ ll of b~ een S and 9.5. Suitable
30 c~ cçs are d;~closed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6,
1984, which ~ Qses fungal cçllul~ce produced from Humicola insolens and
H~nicoln strain DSM1800 or a cç~ e 212-producing fungus bel~n~n~ to the
genus Aeromonas, and cçll~ e extracted from the hepatopallw~as of a marine
mollusk (Dolabella Auricula Solander). Suitable cel~ ces are also disclosed in GB-
CA 0220S412 1997-OS-lS
WO 96/161S5 PCT/US95/14687
26
A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME~) (Novo) is
especially useful.
Suitable lipase enzymes for detergent use include those produced by
microorg~nicm.C of the Pse~ )m~nas group, such as Pseudomonas s~utzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in J~r~nese Patent
Application 53,20487, laid open to public inspection on February 24, 1978. This
lipase is available from Amano Pharm~ce~tic~l Co. Ltd., Nagoya, Japan, under thetrade name Lipase P "Amano," hereinafter lt;relled to as "Amano-P." Other
con~"~e~;ial lipases include Amano-CES, lipases ex Chromobacter vi.~ws~m, e.g.
Chromobacter viscos~-m var. Iipolyticum NRRlB 3673, col-u,,e~cially available from
Toyo Jozo Co., Tagata, Japan; and further Chromobacfer viscosum lipases from U.S.
Bioch~mic~l Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The LIPOLASE~) enzyme derived from H~nicoln
lanuginosa and col,unercially available from Novo (see also EPO 341,947) is a
15 p-erted lipase for use herein.
Peroxidase enzymes can be used in con,bina~ion with oxygen sources, e.g.,
pelca.l,onale, pe.bo-~e, persulfate, hydrogen peroxide, etc. They are used for
"sollltioTl bleaçhi~ " i.e. to prevent "~n~re, of dyes or pigmrntc removed from
substrates during wash operations to other sub~a~es in the wash so' ~tion
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroXi~ce, lignin~c~, and haloperoxidase such as chloro- and bromo-pero~ ce
Peroxidase-cG,.l~h.;..g dele,~;en~ co--.posi~ions are tlicclose~i, for ~-i...plf, in PCT
Intern~tion~l Application WO 89/099813, published October 19, 1989, by O. Kirk
~ccignecl to Novo Industries A/S.
A wide range of enzyme materials and means for their incol~uolalion into
synthetic detergent co.."~osi~ions are also ~licrlQsed in U.S. Patent 3,553,139, issued
January 5, 1971 to McCarty et al. Enymes are further ~icrlosed in U.S. Patent
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, ~ughPs,
issued March 26, 1985. Enzyme materials useful for liquid de~en~ formul~tionc~
30 and their i.,eo,~,u.~ion into such formul~tionc, are ~ic~losed in U.S. Patent4,261,868, Hora et al, issued April 14, 1981. Enzymes foruse in detc~..ls can best~bili7ed by various techniques Enzyrne stabilization teçhn:ques are dicrlosed and
I -e~ ed in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, andEuropean Patent Applic~tion Pllblic~tion No. 0 199 405, Appli~tio~ No.
CA 02205412 1997-05-15
WO 96/1615S PCT/US95/14687
27
86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems
are also described, for example, in U.S. Patent 3,519,570.
Other Ingredients - Usual detersive ingredients can include one or more other
detersive adjuncts or other materials for ~eSieting or enh~n~ing cle~ning pe.rulnlallce~
5 ~ ...e~.l of the substrate to be cle~ned or to modify the ~eethetics of the dt;lel~;e.
composition. Usual detersive adjuncts of d~lelge"l compositions include the
ingredients set forth in U.S. Pat. No. 3,936,537, Baskerville et al. Adjuncts which
can also be in~.iuded in delelgelll compositions employed in the present invention, in
their conventio~l art-est~bliehed levels for use (generally from 0% to about 20% of
0 the detergent ingredients, preferably from about 0.5% to about 10%), include other
active ingredients such as dispersant polymers from BASF Corp. or Rohm & Haas;
color speckles, anti-tarnish and/or anti-corrosion agents, dyes, fillers, optical
brighl~ ~ela~ germicides, alk~tinity sources, h~!dlullopes, anti-oxi~nte~ enzymestabilizing agents, perfumes, solubili7in~ agents, clay soil remolval/anti-redepo~eition
15 agents, carriers, processing aids, pigmlorte solvents for liquid formulations, fabric
softeners, static control agents, solid fillers for bar compositions, etc. Dye Ir~laçer
inhibiting agents, jnclu~in~ polyamine N-oxides such as polyvinylpyridine N-oxide
can be used. Dye-transfer-inhibiting agents are further illustrated by
polyvinylpyrrolidone and copolyrners of N-vinyl imid~ole and N-vinyl pyrroLidcne.
20 If high sudsing is desired, suds boosters such as the Clo-C16 ~ik~nol~nlides can be
incol}Jo~aled into the compositiQ~e, typically at 1%-10% levels. The Clo-C14
monoeth~nol and dieth~nQI amides illustrate a typical class of such suds boosters.
Use of such suds boosters with high sudsing adjunct surf~ nts such as the amine
oxides, b~ ines and sult~ines noted above is also advPnt~geol~c If desired, soluble
25 m~e~inm salts such as MgC12, MgSO4, and the like, can be added at levels of,
typically, 0.1%-2%, to provide ~d~litiQn~l suds and to e~-h~l~ce grease removal
p~;lruln.~c~. .
B~ t;ne~ - Any optical brighten~rs or other brigl.l~ --ing or ~l.;le~.;ng agentsknown in the art can be i.lco.luor~led at levels typically from about 0.05% to about
30 1.2%, by weight, into the dt;le~ conlpoa;liolls herein. Comlne.c;al optical
bl;~hl~ne,a which may be useful in the present invention can be /~ cified into
subgroups, which jnclucl~ but are not neces~l ily limited to, derivatives of stilh~one~
pyrazoline, coumarin, carboxylic acid, ...~lt,;,lecyanines, dibe~.,olt.;l-hen~-5,5-~iQxide~
azoles, 5- and 6-,.,~,..t e~ed-ring heterocycles, and other mi~c~ neoll~ agents.
CA 0220S412 1997-OS-lS
WO 96/16155 PCT/US95/14687
28
Examples of such brighteners are disclosed in "The Production and Application ofFluorescent Brightçning Agents", M. Zahradnik, Published by John Wiley & Sons,
New York (1982).
Specific eY~mples of optical brighterl~rs which are useful in the present
compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on
December 13, 1988. These brightenlors include the PHORW~TE series of
bri~ht~n~rs from Verona. Other brighteners disclosed in this rerelence include:
Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-
10 (4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes;
4,4'-bis(stryl)bisphenyls; and the ~minocoumarins Specific ~,Aa."ples of these
bright~ners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-ven7im~ ol-2
yl)ethylene; 1,3-diphenyl-phrazolines; 2,5-bis(be~-~o~,ol-2-yl)thiophene; 2-stryl-
napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also
15 U.S. Patent 3,646,015, issued February 29, 1972 to ~miltQn. Anionic bri~hlel-e~s
are plert;lled herein.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a poroushydrophobic substrate, then coating said substrate with a hydrophobic co~tin~
20 Plereldbly, the detersive ingredient is a~lmi~ed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is released from
the substrate into the aq~eous washing liquor, where it p~;lrOlllls its ;..l~n-~ed
detersive filnr~tion
To illustrate this te~hn;que in more detail, a porous hydropho~:c silica
25 (trademark SIPERNAT~ D10, Degussa) is ~dmi~ed with a proteolytic enzyme
sohltion con~ p 3%-5% of C13 15 ethoxylated alcohol (EO 7) noniQnic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica.
The res~hing powder is disp.,.~ed with stirring in silicone oil (various silicone oil
vi~cositieS in the range of 500-12,500 can be used). The res~hi~ silicone oil
30 dispersion is emlll~ified or otherwise added to the final d~ltr~e.l~ matrix. By this
means, ingredients such as the aror~..e~.l;oned enzymes, ble~ches, bleach activators,
bleach catalysts, photoactivators, dyes, fluorescel~, fabric conditioners and
hydrolyzable surf~ct~nts can be "~,rote~iled" for use in de~e~ s, in~ in~ liquidlaundry delelgellL compositions.
CA 0220~412 1997-o~
WO 96/16155 PCT/US95/14687
29
Liquid or gel compositions can contain some water and other fluids as
carriers. Low molec~ r weight primary or second~ry alcohols exemplified by
meth~nol, ethanol, propanol, and isop-opanol are suitable. Monohydric alcohols are
pre~"ed for solubilizing surfactant, but polyols such as those con~ from 2 to
5 about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-,o.opanediol,
ethylene glycol, glycerine, and 1,2-propanediol) can also be used. The compositions
may contain from 5% to 90%, typically 10% to 50% of such carriers.
Certain bie~rhinE compositions herein among the generally encomr~e.eed
Iiquid (easily flowable or gel forms) and solid (powder, granule or tablet) fo~ns,
o especially bleach additive compositions and hard surface cle~ninE compositiQnc, may
preferably be form~ ted such that the pH is acidic during storage and ~lk~line during
use in aqueous cleaning operations, i.e., the wash water will have a pH in the range
from about 7 to about 11.5. Laundry and alltQm~tic disl,.vasl~ing products are
typically at pH 7-12, preferably 9 to 11.5. ~ntom~tic dishwashing cQmpo~eitiore~15 other than rinse aids which may be acidic, will typically have an aqueous solution pH
greater than 7. Techniques for controlling pH at lecG.. en~led usage levels include
the use of buffers, alkalis, acids, pHjump systems, dual col,l?~llll.,..L COI.~
etc., and are well known to those skilled in the art. The compositions are useful from
about 5C to the boil for a variety of clç~ninE and ble~chin~ operations.
Ble~chin~ compositions in granular form typically limit water content, for
~mrle to less than about 7% free water, for best storage stability.
Storage stability of bleach compositions can be further nh~nced by limiting
the content in the compositions of adventitious redox-active sul.s~ ces such as rust
and other traces of tr~neitiorl metals in undesirable form. Certain bl~^hinE
comrositions may moreover be limited in their total halide ion content, or may have
any particular halide, e.g., bromide, subs~ lly absent. Bleach st~hili7srs such as
;"~nnAt.~e can be added for improved stability and liquid forrn~ tiQnc may be
ly nC!rl~queol)s if desired.
The following ~ ,lee illustrate the bleach activators of the invention,
i~ les for making same and ble~chinE compositions which can be ~r~ed
using the bleach activators, but are not int~nded to be limiting thereof. All materials
in Fy~mrlee I-X~ satisfy the fimr.tion~l limit~ti~ns herein.
EXAMPLE I
N-[(4-methylsulfonyl)benzoyl] caprolactam:
CA 0220~412 1997-0~
WO 96/16155 PCTtUS95/14687
All glassware is dried thoroughly, and the reaction kept under an inert
atmosphere (argon) at all times.
With stirring, 5.0 g (25.0 mmol) of (4-methylsulfonyl)benzoic acid (Aldrich)
and S.S mL (75.0 mmol) of thionyl chloride (Aldrich, d=1.63 1 g/mol) are added to
5 100 mL tetrahydrofuran (THF - Aldrich, HPLC grade) in a 3-neck round bottom
flask equipped with a reflux condenser, addition funnel, and n~a~c1;c stirrer. The
res--ltin~ reaction mixture is heated to reflux and stirred for 16 h. A~er cooling to
room temperature, the solvent and excess thionyl chloride are removed by
evaporation under reduced pressure. Recryst~11i7~tion of the solid residue from
lo toluene followed by drying under vacuum yields (4-methylsulfonyl)ben_oyl chloride
as a white, crystalline solid.
In a subsequent reaction, 2.33 g (20.6 mmol) of caprolactam (Aldrich) and 2.30
g (22.7 mmol) of triethylamine (Aldrich, d=0.726 g/mol) are added to 50 mL TEIF
(Aldrich, HPLC grade) in a 3-neck round bottom flask equipped with a reflux
15 condlon~or, addition funnel, and m~gnetic stirrer. Addition of a soh-tiQI~ of 4.5Q g
(20.6 mmol) of the (4-methylsulfonyl)-benzoyl chloride in 50 mL THE~ proceeds
dropwise over a period of 30 min, and the resulting reaction mixture is heated to
reflux and stirred for 16 h. Upon cooling to room ter..~ re, the THF is removed
by evaporation under reduced pressure. The solid residue is redissolved in
chloro~l,ll, and extracted several times with D.I. water. The organic layer is dried
over Na2SO4, filtered, concçntrated by removal of solvent, and poured into hexane
to pr~ç;~ e the product. The prt~ e is collected by suction f~ltration, rinsed
with hexane, and dried under vacuum to yield N-[(4-methylsulfonyl)bel~oyl]
caprolactam as a white, crystalline solid.
EXAMPLE II
N-[(4-methylsulfonyl)benzoyl]valerol~ct~m -
Srth~i7çd as for N-[(4-methylsulfonyl)bel~oyl]caprol~ct~m (F--- 1"~ I)
using valerolact~m (Aldrich) in place of caprolactam.
EXAMPLE m
30 N-[(4-ethylsulfonyl)ben_oyl]caprolactam:
The synthesis of N-[(4-ethylsulfonyl)l,~l~oyl]caprolactam proceeds as for N-
[(4-methylsulfonyl)benzoyl]caprol~ct~m (Example I) using (4-ethylsulfonyl)benzoic
acid in place of (4-methylsulfonyl)ben_oic acid.
CA 0220~412 1997-0~
WO 96/16155 PCT/US95/14687
The (4-ethylsulfonyl)ben_oic acid can be synthesi7ed from 2-chloropropionic
acid and 4-(chlorosulfonyl)ben_oic acid according to the procedure of Brown, R. W.
J. Org Chem. 1991, 56, 4974-4976.
EXAMPLE IV
s N-[(4-ethylsulfonyl)benzoyl]valerol~ct~m
Srth~ci7ed as for N-[(4-ethylsulfonyl)benzoyl]caprolactam (Example m)
using valerolactam (Aldrich) in place of caprolactam.
EXAMPLE V
N-[(4-pentylsulfonyl)benzoyl]caprol~ct~m
loSynth~i7ed as for N-[(4-ethylsulfonyl)benzoyl]caprolactam (Example m)
using 2-bromohexanoic acid (Aldrich) in place of 2-chlo- op~opionic acid.
EXAMPLE ~1
N-[(4-pentylsulfonyl)benzoyl]valerolactam:
Synthesi7~d as for N-[(4-pentylsulfonyl)ben_oyl]caprolactam (Example V)
15using valerolactam (Aldrich) in place of caprolactam.
EXAMPLE VII
N-[(4-heptysulfonyl)benzoyl]caprolactam:
Syntheci7ed as for N-[(4-ethylsulfonyl)ben_oyl]caprolactam (Example m)
using 2-bromooctanoic acid (Aldrich) in place of 2-chloropropionic acid.
20EXAMPLE VIII
N-[(4-heptylsulfonyl)benzoyl]valerol~ct~m -
Sy..ll-e~ d as for N-[(4-heptylsulfonyl)benzoyl]capro~ m (F.Y~mple VII)
using valerolactam (Aldrich) in place of caprolactam.
EXAMPLE IX
2s N-(2-furoyl)valerol~ct~m
All glassware is dried thoroughly, and the reaction is kept under an inert
~I...o~ke-e (argon) at all times. With stirring, 20.0 g (0.18 mol) of 2-furoic acid
(Aldrich) and 40.0 mL (0.53 mol) of thionyl chloride (Aldrich, d=1.63 1 g/mol) are
added to 300 mL T~ (Aldrich, HPLC grade) in a single-neck round bottom flask
30 e.luipped with a reflux cond~n~Pr and m~netic stirrer. The rçsulting reactionmixture is heated to reflux and stirred for 16 h. After cooling to room t~ln~ alule~
the solvent and excess thionyl chloride are removed by evaporation under reducedp~S~ul e to yield 2-furoyl chloride.
CA 0220~412 1997-0~
WO 96/161S5 PCTIUS95/14687
In a subsequent reaction, 9.2 g (92 mmol) of valerolactam (Aldrich) and 14.1
mL (101 mrnol) oftriethylamine (Aldrich, d=0.726 g/mol) are added to lS0 mL T~
(Aldrich, ~LC grade) in a 3-neck round bottom flask equipped with a reflux
condenser, addition funnel, and m~nçtiC stirrer. Addition of a solution of 12.0 g (92
mmol) of the 2-furoyl chloride in 150 mL THF proceeds dropwise over a period of
30 min, and the resulting reaction mixture is heated to reflux and stirred for 16 h.
Upon cooling to room temperature, the THF is removed by evaporation under
reduced pressure. The solid residue is redissolved in methylene chloride, and
extracted several times with 5% aqueous hydrochloric and then deioni7ç(l water.
o The organic layer is dried over Na2SO4, filtered, conce~ ed by removal of solvent,
and poured into hexane to preçipit~te the product. The pr~c;~ e is co~ected by
suction filtration, rinsed with hexane, and dried under vacuum to yield N-(2-
furoyl)valerolactam as a white, crystalline solid.
EXAMPLE X
N-(2-furoyl)caprolactam:
Syntheci7ed as for N-(2-furoyl)valerolactam (Example IX) using caprol~t~m
(Aldrich) in place of valerol~ct~m
EXAMPLE XI
N-(3 -furoyl)caprolactam:
Synth~ci7ed as for N-(2-furoyl)caprol~ct~m (Example X) using 3-furoic acid in
place of 2-furoic acid.
EXAMPLE XII
N-(3 -furoyl)valerol~ct~m-
Syntheci7ed as for N-(3-furoyl)caprolactam (Example XI) using valerol~t~m
(Aldrich) in place of caprol~^~t~m
EXAMPLE XIII
N-(S-nitro-2-furoyl)caprol~ct~m
S~ .P c; ~d as for N-(2-furoyl)caprolactam (FY~mple XI) using S-nitro-2-furoic acid
in place of 2-furoic acid.
EXAMPLE XIV
N-(5 -nitro-2-furoyl)valerolactam:
Syntheci7ed as for N-(5-nitro-2-furoyl)caprol~t~m (FY~mrle X~II) using
valerol~ct~m (Aldrich) in place of caprol~ct~m
EXAMPLE XV
~=
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
33
N-(5-bromo-2-fi~royl)caprolactam:
Synthesized as for N-(2-furoyl)caprolactam (Example X) using 5-bromo-2-
furoic acid in place of 2-furoic acid.
EXAMPLE XVI
S N-(5-bromo-2-furoyl)valerolactam:
Synth~si7ed as for N-(5-bromo-2-furoyl)caprol~ct~m (Example XV) using
valerolactam (Aldrich) in place of caprolactam.
EXAMPLE XV~I
N-( l -n~phthoyl)caprolactam:
Synthe~i7ed as for N-(2-furoyl)caprolactam ~Example X) using l-naphthoic
acid in place of 2-furoic acid.
EXAMPLE XVIII
N-( l -naphthoyl)valerolactam:
Synthe~i7ed as for N-(l-naphthoyl)caprol~ct~m (F.Y~mple XVII) using
1S valero!~ct~m (Aldrich) in place of caprol~ct~m
EXAMPLE XIX
N-(3,5-dinitroben_oyl)caprol~ct~m
- = All glassware is dried thoroughly, and the reaction is kept under an inert
atmosphere (argon) at all times. With stirring, 2.33 g (20.6 mmol) of caprolactam
(Aldrich) and 2.30 g (22.7 mmol) of triethylamine (Aldrich, d=0.726 g/mol) are
added to l00 mL toluene (Aldrich) in a 3-neck round bottom flask e~luipped with a
reflux conden~er~ addition funnel, and mech~n;r~l stirrer, to give a clear, pale yellow
solution. ~d~ition of a sol~ltion of 4.75 g (20.6 mmol) of 3,5-di~ "~ben~oyl chloride
(Aldrich) in 100 mL toluene proceeds dropwise over a period of 30 min. The
res--lting reaction mixture is heated to reflux and stirred for 16 h. Upon cooling to
room ttmpelaL~lre~ the reaction is filtered to remove the triethylamine hydrochloride,
and poured into a sepa.~lG.y funnel. A~er dilution with 300 mL of chlolorc,..n, the
organic solution is extracted with 5% aq HCI, 5% aq NaOH, and finally D.I. water.
The organic layer is dried over Na2SO4, filtered, and the solvent removed by
30 evaporation under reduced pressure. Recryst~11i7~tion of the crude product from
toluene followed by drying under vacuum yields N-(3,5-dilul~obel~oyl)caprolactam- as a light yellow, crystalline solid.
EXAMPLE XX
N-(3,5-dilul~ obe~oyl)valerol~ct~m
CA 02205412 1997-05-15
WO 96tl6155 PCTIUS95/14687
Synth~ci7çd as for N-(3,5-dinitrobenzoyl)caprolactam (Example XtX) using
valerolactam (Aldrich) in place of caprolactam.
EXAMPLE X~
N-(3 ,5-dichloroben_oyl)caprol~ct~m
Synth~ci7ed as for N-(4-nitroben_oyl)caprolactam (Example X~II) using 3,5
dichlorobenzoylchloride (Aldrich) in place of 4-niLl obe.~oyl chloride.
EXAMPLE X~I
N-(3,5-dichlorobenzoyl)valerolactam:
Syntheci7ed as for N-(3,5-dichlorobellzoyl)caprolactam (Example X~) using
0 valerolactam (Aldrich) in place of caprolactam.
Examples XX~II-X~ exemplify methods for synth~ci7ing compounds
generically disclosed in prior rerel~i~ces.
EXAMPLE XXIII
N-(4-nitroben_oyl)caprol~ct~m
All glassware is dried thoroughly, and the reaction is kept under an inert
~tmosphçre (argon) at all times. With stirring, 43.0 g (0.38 mol) of caprolactam(Aldrich) and 58.2 mL (0.42 mol) of triethylamine (Aldrich, d=0.726 g/mol) is added
to 150 mL TH~ (Aldrich, HPLC grade) in a 3-neck round bottom flask e~luipped
with a reflux conrl~ncer~ addition funnel, and ,~çl~ c~l stirrer, to give a clear, pale
yellow solution. Addition of a solution of 70.5 g (0.38 mol) of 4-~ lùbel~oyl
chloride (Aldrich) in 100 mL THF proceeds dropwise over a period of 1 h. The
cloudy, dark yellow reaction mixture is heated to refiux and stirred for 16 h.
Upon cooling to room tellll)el~L~Ire, the reaction is filtered to remove the
2S triethylamine hydrochloride, and poured into a se~ala~oly funnel. APcer dilution with
~hlol~rullll, the organic sol~tion is extracted twice 5% aq HCI, twice with 5% aq
NaOH, and finally once with neutral D.I. water. The organic layer is dried over
Na2SO4 or MgSO4, filtered, and the solvent removed by evaporation under reduced
pre~ur~. Recryst~lli7~tion of the crude product from toluene followed by drying
under vacuum yields N-(4-nitrobenzoyl)caprolactam as a light yellow, crystallinesolid.
EXAMPLE X~V
N-(4-nlllobenzoyl)valero!act~m
CA 02205412 1997-05-15
WO 96/16155 PCT/US9S/14687
Synthesi7ed as for N-(4-nitrobenzoyl)caprolactam (Example X~II) using
valerolact~m (Aldrich) in place of caprolactam.
- EXAMPLE XXV
N-(3-nitrobenzoyl)caprolactam:
Syntheci7~Pd as for N-(4-nitroben_oyl)caprolactam (Example X~II) using 3-
nitrobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride.
EXAMPLE XXVI
N-(3-nitrobenzoyl)valerolAct~m
SynthPci7ed as for N-(3-nitrobenzoyl)caprolactam (F.Y~mple XXV) using
valerolactam (Aldrich) in place of caprolactam.
EXAMPLE XXVII
N-(3-chlorobenzoyl)caprol~st~m
SynthPsi~ed as for N-(4-nitrobenzoyl)caprolactam (Example X~II) using 3-
ch~orobenzoyl chloride (Aldrich) in place of 4-nitrobenzoyl chloride.
EXAMPLE XXVIII
N-(3-chlorobenzoyl)valerol~st~m
SynthPci7ed as for N-(3-chlorooben_oyl)caprol~ct~m (Example XXVII) using
valerolact~m (Aldrich) in place of caprolactam.
EXAMPLE X~X
N-(4-chloroben_oyl)caprolact~m
Synthçci7çd as for N-(4-nitrobenzoyl)caprol~ct~m (FY~mrle X~II) using 4-
chlorobenzoylchloride (Aldrich) in place of 4-nitrobenzoyl chloride.
EXA~LE X~
N-(4-chlorobel~oyl)valerol~ct~m
S~thPCi7Pd as for N-(4-chlorobenzoyl)caprola~t~m (FY~ ~.PIe X~ using
~,al~,rQl~Gt~m (Aldrich) in place of caprol~tam
EXAMPLE X~I
RI~Pa~hing con.~o~;l;Qnc having the form of granular laundry dt;le.~e..ls are
30 ~Yemr!ified by the following forrn~ ti.-nc
A B C D E
rNGREDENT % ./ /o % %
BleachActivator~ 5 5 3 3 8
Sod~ r~ o o 19 21 0
=
CA 02205412 1997-05-15
WO 96/161S5 PCT/US9~/146M
36
Sodium r~ onohy~ te 21 0 0 0 20
Sodium P~.l,o.~t~, tetrahydrate 12 21 0 0 0
T~ etylellly~ r o o o l O
~olL~Vylu,.~ O 0 3
Linear aLl~y~ lr-- 7 11 19 12 8
Allyl elllùAyl~t~ (C45E7) 4 0 3 4 6
Zeolite A 20 20 7 17 21
SKS-6~ silicate (Hoechst) 0 0 11 11 0
Trisodium cit~ate - 5 5 2 3 3
Acrylic Acid/Maleic Acid copolymer 4 0 4 5 0
Sodium pOI~aCl~' ~f 0 3 0 3
Di tl.yl~ penta(~ l,yl, ,.e 0.4 0 0.4 0 O
1~1`C~ ; acid)
DTPA 0 0 4 04
EDDS 0 3
CallJu.~ylll~
Protease 1.4 0.3 1.5 2.4 0.3
Lipolase 0.4 0 0 0.2 0
Carezyme 0.1 0 0 0.2 0
Anionic soil release polymer 0 3 0 0 0.4 O.S
Dye transfer inhihi~in~ polymer 0 0 0.3 0.2
Carbonate 16 14 24 6 23
Silicate 3.0 0.6 12.5 0 0.6
Sulfate, Water,Perfilme,Cl~ ' to 100 to 100 to 100 to 100 to 100
*Bleach activator according to any of Exanlijles I - X~
Any of the above. compositions is used to launder fabrics under "high soil"
con.lition~ "High soil" con.lition~ are achieved in either of two possible modes. In a
first mode, con~ .er bundles of heavily soiled fabrics can be used, the soil level
5 being s~fficiently high that when a portion of the co...i.os;l;on is dissolved in the
pl~isence of tap-water together with the soiled fabrics in a U.S. domestic w~hing-
m~hine, the pH of the wash water is in the range from about pH 6.5 to about 9.5,more typically from about 7 to about 9.5. Alternatively, it is convenient for testing
purposes when heavily soiled fabrics are unavailable, to use the following procedure:
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
37
the pH of the wash bath a~er dissolution of product and addition of the test fabrics is
adjusted using aqueous HCI such that the pH is in the range from about pH 6.S toabout 9.S. The test fabrics are a lightly soiled or clean bundle of consumer fabrics;
additional test swatches of fabric comprising bleachable stains are typically added. In
5 general in the present example, the product usage is low, typically about 1000 ppm
col-ee..l . ~lion of product in the wash.
The fabrics are washed at about 40C with e~c~ f~nt results, particularly with
respect to ble~çl in~ as co.nl)ared with otherwise idçrltic~l co"~ osilions in which
TAED, NOBS or benzoylcaprol~ct~m are used at equal weight as a ~epl~e-n~ .l for
0 the *-identified bleach activator. In particular, novel pe,ru-..,al~ce-çnh~n~ed bleach
activators such as those of Examples III-XII provide superior results and are highly
;d.
Additional granular laundry detergents having nonionic surfactant systems are
15 exemplified by the following formulations; they are test~d as dese il,ed supr-..
F G ~ I
INGREDIENT % % % /
Bleach Activator* S 3 6 4.5
Sodium Pe.~- 20 21 21 21
Tclr~acetyl~ ,v 0 6 0 0
~ lo,~ 4.5 0 0 4.5
Alkyl ClllOA,~Iat~. (C45E7) 2 5 5 5
N-cocoylN-methYI i - ~
ZeoliteA 6 5 7 7
SKS-6~ silicate (Hoechst) 12 7 10 10
T s ' citrate 8 5 3 3
Aclylic Acid/Maleic Acid copolymer 7 5 7 8
(partially r....1..1;,. d)
D~ f-- Il;---';l~f~' penta(,~ l"',~ ~ 0.4 0 0 0
ph~,~ph~ acid)
EDDS 0.3 0.5 0-5
UA~ f;ll .~ 0 0.4 0 0
Protease 1.1 2.4 0.3 1.1
CA 02205412 1997-05-15
WO 96/16155 PCTIUS95/14687
38
Lipolase 0 0.2 0 0
Carezyme 0 0.2 0 0
Anionic soil release polvmer 0.5 0.4 0.5 0.5
Dye transfer i.~ ;i.e polymer 0.3 0.02 0 0.3
Carbonate 21 10 13 14
Sulfate, Water, Perfume, C~!~ to 100to 100 to 100 to 100
*Bleach activator according to any of Examples I to X~.
EXAMPLE X~I
This Example illustrates cle~ning compositions having bleach additive form,
s more particularly, liquid bleach additive compositions in acco-dance with the
nvention.
A B C D
Ingredients wt% wt% wt% wt%
NEODOL 91-101 6 5 7 4
NEODOL45 71 6 5 5 8
NEODOL 23-21 3 5 3 3
DEQUEST 20602 0.5 0.5 1.0 1.0
Bleach Activator3 6 6 4 7
Citric Acid 0.5 0.5 0.5 0.5
NaOH to pH 4 to pH 4 to pH 4 to pH 4
Hydrogen Peroxide 7 3 2 7
Water Ral~n~e R~l~n~e R~l~n~e Ral~nce
to 100%to 100% to 100% to 100%
1 Allcyl ethoxylate available from The Shell Oil Company.
2 Co~ ;ally available from ~onc~nto Co.
3 Bleach Activator according to any of Ex~mrlPc I-X~.
E F G
Ing,tdie~ wt % wt % wt %
Water to 100% to 100% to 100%
NEODOL 91-101 10 10 10
NEODOL 23-21 5 5 5
CA 02205412 1997-05-15
WO 96/161S5 PCT/US9~/14687
39
DEQUEST 20102 0.5 0.5 1.0
Bleach Activator3 4 4 8
Citric Acid 0.5 0.5 0.5
NaOH to pH 4 to pH 4to pH 4
Hydrogen Peroxide 7 5 5
1 Allyl ethoxylate available from The Shell Oil Company.
2 Commercially available from Monsanto Co.
3 Bleach activator according to any of Examples I-X~.
The compositions are used as bleach ~oosting additive (to be used in
s ADDITION to a bleach OR non-bleach detergent such as TIDE~) in a wash test
otherwise similar to that used in Example X~. The additive is used at 1000 ppm,
and the cor..".e..iial deler~e--t is used at 1000 ppm.
EXAMPLE X~II
This Fy~mple illustrates cle~ni~ compositions having bleach additive form,
10 more particularly, liquid bleach additive compositions without a hydrogen peroxide
ource in accolddnce with .he invention.
A B C D
Ingredients wt % wt % wt % wt %
NEODOL 91-101 6 5 7 10
NEODOL 45-71 6 5 5 0
NEODOL 23-21 3 5 3 5
DEQUEST 20602 0.5 0.5 1.0 1.0
Bleach Activator3 6 6 4 7
Citric Acid 0.5 0.5 0.5 0.5
NaOH to pH 4 to pH 4 to pH 4 to pH 4
Water Ral~nce Ral~nce Ral~nce R2l~nce
to 100% to 100% to 100% to 100%
1 Allyl ell~o~lale available from The Shell Oil Company.
2 Comrnercially available from Mon~nto Co.
3 Bleach Activator acco.ding to any of FY~mp~nr I-X~.
lS The compositions are used as bleach boosting additive (to be used in
ADDITION to a bleach detelge.~t such as TIDE~ WITH BLEACH) in a wash test
CA 02205412 1997-05-15
WO 96/16155 PCT/US9S/14687
otherwise similar to that used in Example X~I. The additive is used at 1000 ppm,and the cornmercial detergent is used at 1000 ppm.
EXAMPLE X~IV
Bleaching compositions having the form of granular laundry detergents are
5 exemplified by the following formulations.
A B C D E
INGREDENT % % /o % /
sleach Activator* 5 s 3 3 8
Sodium r~ 0 S lS 0 0
Sodiumr. .l,. ~t l--onol-~ t~' 5 0 0 10 20
Bli~ht~ . 49 04 0-4
NaOH 2 2 2 o 2
Linear aL~y~ r~ partially 9 9 9 9 g
i7~'d
Allyl ethoxylate (C25E9) 7 7 5 4 6
Zeolite A 32 20 7 17 21
Acrylic Acid/Maleic Acid co~l~ . o o 4 5 8
Sodium polya~ly~ 0.6 0.6 0.6 o o
Di_lh,~ler.~,hi~l.ine penta(rl.,ll-,~l~.. -e 0.5 0 O.S O
pk..~,h .~ acid)
EDDS O O.S O O.S O
Protease I 1 1.5 2.4 03
Lipolase o o o 0.2 0
Careyme o o o 0.2 o
Anionic soil release polymer o o o.s 0.4 0.5
Dye tran~er inhi~itin~ polymer o o 0.3 0.2 o
Soda Ash 22 22 22 22 22
Silicate (2r) 7.0 7.0 7.0 7.0 7.0
Sulfate, water, Perfume, C~!~ to loo to 100 to 100 to loo to loo
*Bleach activator accordil)g to any of FY~mrl~s I - X~
Any of the above compositions is used to launder fabrics under rnildly alkaline
Col~ ;Ql~c (pH 7 - 8). The pH can be adj~-cted by altering the plopo,~ion of acid to
Na- salt form of alkylben7~neslllfonate.
CA 02205412 1997-05-15
WO ~6/16155 PCT/US95/14687
41
Fabrics are washed at about 40C using a concentration of about 1000 ppm of
the composition with excellent results, particularly with respect to b'cachin~ as
con~pal ed with otherwise identical compositions in which TAED, NOBS or
benzoylcaprolactam are used at equal weight as a repl~c~om~nt for the pe.ro..--ance-
5 enh~nced bleach activator. In particular, novel performance-~nh~nced bleach
activators, such as those of Examples III-X~I, provide superior results and are highly
pl ~r~ d.
EXAMPL~ X~V
==A cle~nin~ composition ~esiEned for use as a granular bleach additive is as
follows:
In~redient % (wt.)
Bleach Activator* 7.0
Sodium Perborate (monohydrate) 20.0
Chelant (DTPA, acid form) 10.0
Citric Acid (coated) 20.0
Sodium Sulfate R~ n~e
*Bleach Activator according to any of Ex~mrlec I-X~.
In an alternate embo-liment the composition is modified by replacin~ the
sodium perborate with sodium percarbonate.
EXAMPLE X5~VI
Cleaning co.nposiLions having liquid form especially useful for cle~ning
bathtubs and shower tiles without being harsh on the hands are as follows:
Ingred.el,l % (wt )
A B
2S Bleach Activator* 7.0 5.0
Hydrogen reroAide 10.0 10.0
C12AS, acid fo~n, partially neutralized 5.0 5.0
C12 14AE3S, acid form, partially neutralized 1.5 1.5
C12 DimethylArnine N-Oxide 1.0 1.0
DEQllEST 2060 0.5 0.5
Citric acid S.5 6.0
Abrasive (15-25 micrometer) 15.0 o
HCL to pH 4
Filler and water R~l~nre to 100%
CA 0220~4l2 lgg7-o~
WO 96/16155 PCT/US95/14687
42
*Bleach Activator according to any of Examples I-X~.
EXAMPLE X~VII
A granular automatic dishwashing dele,~el~l composition comprises the
follow~ng.
A B C D
INGREDIENT wt% wt% wt ~O wt %
Bleach Activator (See Note 1) 3 4-5 2.5 4.5
Sodium ~e.l Gr~le Monohydrate (See Note 2) 1.5 0 1.5 0
Sodium Pe,-ia,boriale (See Note 2) 0 1.2 0 1.2
Amylase (TERMAMYL~9from NOVO) 1.5 2 2 2
Dibenzoyl Peroxide 0 0 0.8 0
T,~nsilion Metal Bleach Catalyst (See Note 3) 0 0.1 0.1 0
Flulease (SAVINASE E9 12 T, NOVO, 3.6% active protein) 2.5 2.5 2.5 2.5
Trisodium Citrate Dihydrate (anhydrous basis) 7 15 15 15
Citric Acid 14 0 0 0
Sodium Bicarbonate 15 0 0 0
Sodium Ca,l,onale, anhydrous 20 20 20 20
BRITESIL H203, PQ Corp. (as SiO~) 7 8 7 5
Diethyl~nel,ia"linepenta(methylenephosphonic acid), Na 0 0 0 0.2
Hydroxyethyldiphosphonate (HEDP), Sodium Salt 0 0.5 0 0.5
Ethylonedia",i"e~;,Jcr,inate, Trisodium Salt 0.1 0.3 0 0
D;spc:,:.a,,l ~oly."er (Accusol 480N) 6 5 8 10
~ ~ n;O,l.C Surfactant (LF404, BASF) 2.5 1.5 1.5 1.5
Paraffin (Winog 70~)) 1 1 1 0
Ben~ot,- ~'e 0.1 0.1 0.1 0
SodiumSulfate,water,minors BALANCETO: 100% 100% 100% 100%
Note l:Bleach Activator a~o,.ling to any of F . ~ I -XXX.
Note 2: These ~,g~n peroxide sources are e~ ~d on a weight % available oxygen basis. To
convert to a basis of ~.~,c~æc of the total . - divide by about 0.15.
Note 3:Transition Metal Bleach Catalyst: MnEDDS ~ g to U.S. ~L.~ Ser. No.
08/210,186,filedMarchl7, 1994.
EXAMPLE x~vm
CA 02205412 1997-05-15
WO 96/161S5 PCT/US95/14687
A commercial rinse-aid block sold as "Jet-Dry" is modified as follows: The
rinse aid block and about 5% - 20% of a bleach activator according to any of
Examples I-X~ are comelted, mixed and resolidified into block form. The
rPs~lting cleaning composition is used in an automatic dishwashing appliance with
5 exc~ nt spotting/filming and stain removal results.
EXAMPLE X~X
Liquid ble~ching compositions for cle~ning typical hou.~ellol11d surfaces are asfollows. The hydrogen peroxide is separated as an aqueous solution from the other
components by a suitable means such as a dual ch~mber col~Lail~er.
Component A B
(~vt %) (wt %)
C~ E~ nonionic surfactant 20 15
Cl? l~E~ nonionic surfactant 4 4
C8 alkyl sulfateanionic 0 7
surfactant
Na2CO~/NaHC0~ 1 2
Cl ?_l ~ Fatty Acid 0.6 0.4
Hydrogen peroxide 7 7
Bleach Activator* 7 7
Dequest 2060** 0 05 0 05
H?O Balance to 100 R~l~nce to 100
0 * Bleach Activator accGrliing to any of Examples I-X~.
**cG~ cl~ially available from ~on~nto Co.
EXAMPLE XXXX
A.laundry bar suitable for hand-washing soiled fabrics is ple"~ed by standard
extrusion processes and comprises the following:
lS . Component Weight %
Bleach Activator acco,dil.g to any of FY~mples I-X~ 4
Sodium Pclbol~e Tetrahydrate 12
C12 linear alkyl benzene sulfonate 30
phosph~te (as sodium tripolyph~sph~te) 10
Sodium c~l,or.a~e 5
Sodium pyrophosphate 7
CA 02205412 1997-05-15
WO 96/16155 PCT/US95/14687
4~
Coconut monoethanolamide 2
Zeolite A (0.1-lO micron) 5
Carboxymethylc~llnlose 0.2
Polyacry!ate (m.w. 1400) 0.2
BrightPner, perfume 0.2
Protease 0 3
CaS04
MgSO4
Water 4
o Filler* R~l~nceto 100%
*Can be s~lected from convenient materials such as CaCO3, talc, clay, .~ tes~ and
the like. Acidic fillers can be used to reduce pH.
Fabrics are washed with the bar with eycpllent results.
