Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITON
Technia-l Pield
The present invention relates to a dete~ nt cG~ ~c;tion comprising phoLoble;~ch, a non-
AQA surfactant and a bis-alkoxylated quate,-la~y q. ~ oniu~ (bis-AQA)c?tionic
10 ~ulf~ctant.
~und to the Invention
The formulation of laundry dete.genLs and other cleDning co~ nc p~sents a
15 con~;dP-rable chqllen~e~ since modern co.. I~sitionc are ,~uired to remove a variet,v of
soils and stains from diverse substrates. Thus, laundry d~t~ .E,ent~ hard surface
cleanc~, chDmpoos and other pe.~nal cle~ncing c~ po~;~;or~c~ hand dishwc.sh.ng
d~t~rgenl~ and deL~.gent cou~ ;Qnc suitable for use in automatic dishwashers allrequire the proper se~ ;0l- and combination of ingredients in order to function
20 effectively. In g~el~e~l~ such d~tcrg~nt col~positions will contain one or more types of
surf ~t~ntc which are designed to loosen and remove dif~rent types of soils and stains.
While a review of thc lit~ ul~ would seem to indi~atP that a wide sçle~tion of
surf~tDntc and surfactant cGlnkin~;ollc are available to the dete~gent manufacturer, the
reality is that many such ingredients are s~i~lity ch~rni~lc which are not suitable in
25 low unit cost items such as home-use laundry dete~,ents. The fact remains that most
such home-usc ~ such as laundry detelg~;nls still mainly co",l,.i~ one or more of
the con~ t;on~l etho~cylated nonionic and/or s~llfated or sulfonated anionic surfaet~ntc,
e~ ly due to c~nv~o .;c c~ncidçrations and the need to formulate co"~ ;onc
which function l~n~bly well with a variety of soils and stains and a variety of
30 fabrics.
The lite~alule ~ug~-~ jtC that various niL,~gen-cont~ining c~tionic surfart~ntc would be useful
in a variety of clYnin~ c~lnpositir)nc Such materials, typically in the form of amino-,
amido-, or quaternary ammonium or imi~i~701inium colllpounds, are often designed for
35 c~i~lity use. For e~mrle, various amino and quaternary ~mmonium surf~rt~n~c have
been suggested for use in shampoo compositions and are said to provide cosmetic benefits
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to hair. Other nitrogen-cont~inin~ surfart~ntc are used in some laundry detc.gen~ to
provide a fabric softening and anti-static benefit. For the most part, however, the
conl~ue--;ial use of such materials has been limited by the difflculty encountered in the large
scale m~nllfactllre of such compounds. An additional limitation has been the potential
S plecipiLation of anionic active colllpollcn~ of the detelge,l~ composition occasioned by their
ionic interaction with cationic sul r~ . The afor~ tioned nonionic and anionic
surf~t~ntc remain the major surfactant COIll~Ol~ s in today's laundry compositions.
The quick and efficient removal of different types of soils and stains such as body soils,~0 greasy/oily soils and certain food stains, can be problematic. Such soils comprise a
re of triglycerides, lipids, complex polysaccharides, il~lg~ic saltc and p.ute;~ eo!.c
matter all of which, are to some extent, composed of hydrophobic moieties and are thus
notoriously ~iffi~.llt to remove. Low levels of hydrophobic soils and residual stains often
remain on the surface of the fabric after washing.
A wide variety of bk~Ch~s~ for example peroxygen bleach, chloride bleaches and
photobleaches are commonly used in dct~.~enl conlpo~ilions in addition to ~ulr;-c~ ts as
mPntion~A above. Photobleachs are conv~ ,I;o~ y used under ch~ l;.n~es where
launde~ed fabrics are subjected to coll,el~ t,d light sources, such as direct s~mlight as in a
20 line drying operation. Photobleach is a relatively mild bleach particularly effective at
decolouration of coloured pig.. 1~ (e.g. in particulate or beverage stains) and removal of
colour from the organic residues associated with body soils. The blP ~r~ power of the
photobleach is derived from e~"~s.lle to ultra violet s~mlight It is believed that sunlight
converts the photobleach into an active bk~fhi~ species which then oxidises coloured
25 stains present on the fabric. One ploble.ll associated with the use of any
blesch, i.~ln~ the pholobleach is the inability to completely remove residual soil and
stain from the surface of the fabric. Sl~ccescive washing and wearing coupled with limited
soil removal in the wash c~lmin ~.~S in a build up of residual soil and stain which further
entraps particulate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy
30 al,~a~ ce which is perc ~ ed as ~l~e~able and discarded by the col~uule~.
It has been discovered that certain bis-alkoxylated quate~ ammoniwn (bis-AQA)
col.lpounds can be used in various dete.~~ compositions to boost detelgen~r pelrollllance
on a variety of soil and stain types, particularly the hydrophobic soil types, comrnonly
35 cllcc~ullleled. Une~ecledly, it has now been discovered that compositions cont~ining bis-
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AQA surf~t~ntc and photobleach deliver superior cleal~ing and whiten~ss pelrolllldnce
versus products contAinin~ either technology alone.
The bis-AQA surfact~ntc of the present invention provide substantial ~n.rl~ to the
S fonnulator, over cationic surf~t~ntc previously known. For example, the bis-AQA
~ul r~ used herein provide marked improvement in cle~nin~ of "everyday" greasy/oily
hydrophobic soils regularly el~counl~ed. Moreover, the bis-AQA surf~rt~ntc are
co..lpatible with anionic surfaçt~ntc comnlonly used in deterg~"lt colll~osilions such as alkyl
sulfate and alkyl be.~e,~ sulfonate; hlcollllJalibility with anionic cOI~ .lLs of the
10 dete.gf .-l composition has commonly been the limiting factor in the use of c~ti~nir
~ulr~tA~c previously known. Low levels (as low as 3 ppm in the h.lllde.ing liquor) of
bis~AQA SUrraCI~n~c gives rise to the ~n,rlL~ des~libed herein. Bis-AQA surf~rt~ntc can
be form~ ~d over a broad pH range from S to 12. The bis-AQA ~u r~ can be
p~. d as 30% (wt.) solutions which are ~ hle, and Ille~fu~ easy to handle in a
15 m~ml~ l.-. hlg plant. Bis-AQA s~ r~e~ with degrees of ethoxylation above 5 are
SOI~f,~ f S present in a liquid form and can Ll.~ fore be provided as 100% neat materials.
In addition to their beneficial h~n~ling plo~lLies, the availability of bis-AQA surf~rt~ntc as
highly conce.ltlatLd solutions provides a s~b~ l econol.lic advantage in Lldns~lL~tion
costs. The bis-AQA ~wr~ n~ are also col~-p~;hlE with various ~.rullle ingredients,
20 unlike some cationic surfi~ct~ntc known in the art.
It is believed that the greasy/oily soils are effectively solubilized by bis-AQA, ILe.,_b~
allowing access of the photobleach to the colour bodies in the soil (e.g. e.l~rdp~cd
P;r"-~ ls) res~ltin~ in improved soil decolouration. The present invention thus provides a
25 detefgelll co~ o ;l;on which not only delivers superior cle~ning of both hydruphobic
greasy/oily soils and h~r~ol)hilic coloured soils by way of a dete.~.ll colll~o~ilion
col~ g a bis-AQA surfactant and a photobleach.
BACKGROUND ART
U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates
to anionic/c~tionir sulrac~t ll~uLIules. U.K. 2,040,990, issued 3 Sept., 1980, to A. P.
Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry
de~.gcnts.
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Summary of the Invention
The present invention provides a composition co,llp,isil1g or pl~tJar~,d by combining a
photobleach, non-AQA surfactant and an effective amount of a bis-alkoxylated quat. ~ y
S ~~ -onium (bis-AQA) cationic sulri c~nt of the formula:
R~ /A~R
N\ X
R2/ A qR
wh~ in Rl is a linear, bl~ched or sl~bstitlltçd Cg-C1g alkyl, aL~cenyl, aryl, aLkaryl, ether or
10 glycityl ether moiety, R2 is a Cl-C3 aL~cyl moiety, R3 and R4 can vary i lde~ ntly and are
select~ from hydlogen, methyl and ethyl, X is an anion, and A and A' can vary
infl. ~.~ 1y and are each Cl-C4 aLlcoxy, p and q can vary inf~e~ and are i~ ,ge~a of
from 1 to 30.
Detailed Des~ tion of the In~ ion
Photobleach
The co.ll~osilions of the present i~ve~,lion Culll~,lisc a photobleach as an esse;~ l feature
20 thereof. Photobleaches suitable for use herein include sulfonated zinc and/or qhl...i..;.....
phthalo~;y~ilKs. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. The
phthalo~ e photobleaches are available for e~"ple under the lui-~e ~lllf TINOLUX or
as zinc phthql~anine sulfonate.
25 In general the phthql~ ines can be pn,parcd in the ll~mel descril)ed by T.in~te,q~d and
co~o,~ , as ~.t~d in "Journal of the Ch~mi~ql Society" (pl719,1936). As is well
lcnown, ~ b~ te~ metal phthalocyanines are soluble in water to an nmlcllqlly lowdegree and are ~ .,fo.e used as pi~ f.~C. However water solubility can be improved by
the introduction of h~dlophilic groups such as sulfo, carboxy, or other sl~ctit~ent groups
30 into the phthalocyanine s~ ule by the use of hot oleum. Sulfonated phthalocyanines are
useful dyes because they have an affmity for cellulose in the form of either cotton or paper
pulp.
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As noted hereinabove, phthalocyanines can be readily sulfonated by heating with oleum.
Thus zinc and aluminium phthalocyanines which are monosulfonated, disulfonated,
trisulfonated and tetrasulfonated can be prepared. The trisulfonated and tetrasulfonated
S species are p.er~lred for use as photobleaches. The zinc tetrasulfonated and zinc
trisulfonated phthalocyanines are most pr~f~,l~d.
Detergelll compositions employed herein contain from 0.025 % to 1.25 % by weight, of
such bleaches.
Bis-Alkoxvlated Ouatel,.aly A~ ,ol~iLu~, (bis-AOA) Cationic Surfactant
The second essc.~ l Coll~ of the present invention COlllpliSCS an effective ~mollnt of a
bis-AQA ~ulr~ll of the formula:
R~ /ApR
N\ X
R2/ A qR
wherein Rl is a linear, bl~lchcd or subsli~u~d alkyl, alkenyl, aryl, alkaryl, ether, glycityl
ether moiety cont~ini~ from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most
20 preferably from 8 tol4 carbon atoms; R2 is an allcyl group cont~ining from 1 tO 3 carbon
atoms, preferably methyl; R3 and R4 can vary independently and are selecte~ from the
group co..~ g of hydrogen (pl~f~ d), methyl and ethyl; X~ is an anion such as
chloride, l~l~o.l.ide, methyl sulfate, sulfate, S--r~ to provide electrical neutrality. A and
A' can vary i~ epr ~ntly and are each selected from Cl-C4 aLkoxy, especially ethoxy,
propoxy, butoxy and ~ lUl~,S thereof; p is from 1 to 30, p,e~e~bly 1 to 15, morepreferably from 1 to 8, even more preferably 1 to 4 and q is from 1 to 30, preferably 1 to
15, more preferably from 1 to 8, even more plefe~ably 1 to 4. Most preferably both p and
qare 1.
Bis-AQA compounds wllcle~ t_e l~dloc~lJyl substituent R1 is Cg-C12, especially Cg-
C1o, el-hA.-~e the rate of dissolution of laundry granules, especially under cold water
conditions, as com~,~cd with the higher chain length materials. Accordingly, the Cg-C12
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bis- AQA surfartAntc may be preferred by some formulators. The levels of the bis-AQA
surfactants used to prepare finich~od laundry del~.gelll compositions can range from 0.1% to
5%, typically from 0.45% to 2.5%, by weight. The weight ratio of bis-AQA to
pe.. all~onate bleach is in the range of from 1:100 to 5:1, preferably from 1:60 to 2:1, most
preferably from 1: 20 to 1:1.
The present invention employs an "effective amount" of the bis-AQA surfartAnt.~ to
improve the pc.ro~ alue of cle~ning col.lpo~;~ions which contain other optional
ingredients. By an "effective amount" of the bis-AQA surf~t~nt~ herein is meant an
~mollnt which is sufficient to improve, either directio~lly or si~ llirlc~llly at the 90%
confi~lenre level, the ~.rolllla~ce of the cle~ning composition against at least some of the
target soils and stains. Thus, in a composition whose targets include certain food stains,
the formulator will use sufficient bis-AQA to at least directionally irnprove cle~nin~
~lr~/llllance against such stains. Likewise, in a colllposilion whose targets include clay
soil, the fonn~ tor will use s~fflieient bis-AQA to at least directionally improve cle~nir~
.rl,lll~ce against such soil.
The bis-AQA s~ may be used in colllbi~dlion with other detersive surf. ~t~ntc- at
levels which are erf~,~,live for achieving at least a directional improvement in cleaning
~.Ç.llllallce. In the context of a fabric laundry composition, such "usage levels" can vary
~pen-ling not only on the type and severity of the soils and stains, but also on the wash
water t~.ll~dl~lre, the volurne of wash water and the type of washing ,ll~rki"r.
For example, in a top-loading, vertical axis U.S.-type automatic washing m t-hin~ using 45
to 83 liters of water in the wash bath, a wash cycle of 10 to 14 minll~çs and a wash water
lC~ ~.d~ of 10~C to 50~C, it is pfer.,.l~d to include from 2 ppm to 50 ppm, preferably
from 5 ppm to 25 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of
usage rates of from 50 ml to 150 ml per wash load, this tr~nc~tçs into an in-pr~lu._l
co~ c llrdlion (wt.) of the bis-AQA sulra.;~l.L of from 0.1% to 3.2%, preferably 0.3% to
1.5%, for a heavy-duty liquid laundry det.,.~el~t. On the basis of usage rates of from 60 g
to 95 g per wash load, for dense (ncompact") granular laundry de~lge.lts (density above
650 g/l) this trAncl~t~çs into an in-product concentration (wt.) of the bis-AQA surfactant of
from 0.2% to 5.0%, preferably from 0.5% to 2.5%. On the basis of usage rates of from
80 g to 100 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this
.. . . . .
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translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1 % to
3.5 %, preferably from 0.3 % to 1.5 % .
For example, in a front-loading, horizontal-axis European-type automatic washing mq-rhinlo
5 using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 ...i.~ ,s and a
wash water Lel,l~.dl~re of 30~C to 95~C, it is p~ d to include from 13 ppm to
900 ppm, preferably from 16 ppm to 390 ppm, of the bis-AQA surfactant in the wash
liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this trqn~lqtrs
into an in-product collcenllation (wt.) of the bis-AQA surfactant of from 0.4% to 2.64%,
10 preferably 0.55% to 1.1%, for a heavy-duty liquid laundry dele.~ L. On the basis of
usage rates of from 40 g to 210 g per wash load, for dense (ncompact") granular laundry
dete.gen~ (density above 650 g/l) this trqnClqtes into an in-product collcentldlion (wt.) of
the bis-AQA s-llracta,l~ of from 0.5 % to 3.5 %, preferably from 0.7 % to 1.5 %. On the
basis of usage rates of from 140 g to 400 g per load for spray-dried granules (i.e., "fluffyn;
15 density below 650 g/l), this trqnCl~-e~ into an in-plo l-lcl concelltlàlion (wt.) of the bis-
AQA surfactant of from 0.13% to 1.8%, preferably from 0.18% to 0.76%.
For example, in a top-loading, vertical-axis Japa~-~se type ~ ..AI;c washing ...~h;..r
using 26 to 52 liters of water in the wash bath, a wash cycle of 8 to 15 ...;.~ s and a wash
20 water te,ll~.dl-lre of 5~C to 25~C, it is plef~ d to include from 1.67 ppm to 66.67 ppm,
preferably from 3 ppm to 6 ppm, of the bis-AQA surfactant in the wash liquor. On the
basis of usage rates of from 20 ml to 30 ml per wash load, this tranclqtes into an in-product
conc~.lL.dlion (wt.) of the bis-AQA surfactant of from 0.25% to 10%, preferably 1.5% to
2%, for a heavy-duty liquid laundry dct.~ . On the basis of usage rates of from 18 g to
35 g per wash load, for dense (nco.. ,~ cln) granular laul~dry dc;ler~e~t~ (density above 650
g/l) this translates into an in-product CO~ dtiOll (wt.) of the bis-AQA surfactant of from
0.25% to 10%, preferably from 0.5% tol.0%. On the basis of usage rates of from 30 g to
40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this tr~nCl?tes
into an in-product col~cenLIdlion (wt.) of the bis-AQA surfactant of from 0.25% tolO%,
30 preferably from 0.5% to 1%.
As can be seen from the for~goillg, the amount of bis-AQA surfactant used in a m~rhin~-
wash laundering context can vary, depending on the habits and practices of the user, the
type of washing m~cllin~. In this context, however, one heretofore unappreciated35 advantage of the bis-AQA surfact~ntc is their ability to provide at least directional
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improvements in l)c~ro~ dl ce over a sl,e,~ of soils and stains even when used at
relatively low levels with respect to the other surf~rt~ntc (generally anionics or
anionic/nonionic mixtures) in the finich.o-l compositions. This is to be distinguished from
other compositions of the art wherein various cationic surf~rt~n-c are used with anionic
S surfact~ntc at or near stoichion~el,ic levels. In general, in the practice of this invention, the
weight ra~io of bis-AQA:anionic surfactant in laundry compositions is in the range from
1:70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably 1:15
to 1:8. In laundry co,,,yosilions which con,~ise both anionic and nonionic surfact~ntc, the
weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, ~., f~.dbly 1:50 to 1:8.
Various other cle~ning coml~osilions which colll~lise an anionic aulra~ , an optional
nonionic surfactant and specialized aul~-gc~nlc such as betaines, svlt~inlos, amine oxides can
also be form~ t~d using an effective ~mmmt of the bis-AQA surf:~t~ntc in the l.lalllKr of
15 this invention. Such co,.,l~osil;on~ include, but are not limited to, hand dishwashing
products (especi~lly liquids or gels), hard surface cleaners, shampoos, pe,~ol~al cle~ncing
bars, laundry bars, and the like. Since the habits and practices of the users of such
ColllpOsiliG~I5 show ~ /~ialiOn, it is satisfactory to include &om about 0.25% to
about 5%, preferably &rom about 0.45% to about 2%, by weight, of the bis-AQA
20 surf ~t~nts in such co,~oailions. Again, as in the case of the granular and liquid laundry
composition., the weight ratio of the bis-AQA surfactant to other surfi ~t~ntc presen~ in
such composilions is low, i.e., sub-sloichiolll ~ic in the case of anionics. Preferably, such
cle~nin~ compositions co,J~ise bis-AQA/surfactant ratios as noted immP~ trly above for
in~ use laundry co,,,posilion~.
In co,l~,~l with other c~ nir surf~t~ntc known in the art, the bis-aLkoxylated cationics
herein have S-~rr.ri~ solubility that they can be used in combination with mixed surfactant
S~at~ s which are quite low in no"io~ic surf~t~nts and which contain, for example, alkyl
sulfate ~ul G.( ~n~. This can be an il..~ ~ll consideration for formulators of de~erge,
30 c~,l"~osilions of the type which are conve.llionally ~esign~i for use in top loading
o~ ;r washing ~ rl~ 5, especi~lly of the type used in North America, as well as
under Jap~n~e usag col~dilions. Typically, such compositions will comprise an anionic
au.r~ nonionic surfactant weight ratio in the range from about 25:1 to about 1:25,
preferably about 20:1 to about 3:1. This can be contrasted with E~o~an-type formulas
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which typically will comprise anionic:nonionic ratios in the range of about 10:1 to 1:10,
preferably about 5:1 to about 1:1.
The preferred ethoxylated cationic surf~rt~ntc herein are available under the trade name
S ETHOQUAD from Akzo Nobel Ch~mi~qlc Company. Alternatively, such materials can be
5y~ f s-~d using a variety of dirr~fc.~ ,aclion sch~-.-rs (wl~c~ l "EO" r~ escn~-CH2CH2O- units), as follows.
SCHEME 1
RIOH + N H3 H2/Cat/Heat ,Rl N ~H
EXC ES S
Rl N~ + 2 n~ BASECat, Rl N--[(EO)nH~2
Rl N--[(EO)nH]2 + CH3CI ~Rl Nl--[(EO)nHk
CH3 cr
SCHEME 2
'N--[(EO)2Hk + C H2/Cat, ~N--[(EOkH]2
RlBr + N--[(EO)2H~2 HEAT, Rl Nl--[(EO)2H]2
CH3 Br
SCHEME 3
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WO 97143394
[( 2 ]2 H' 'H HÉAT
R~Br ~N--[(EO)2Hl2 HEAT ~ R--I--[(EO)2Hk
CH3 Br
SCHEME 4
Cl--CH2CH2--OH + n~ ~ Cl--CH2CH20[EO~n--~
R--N~cH + 2 Cl--CH2CH20[EO]n--H ~ Rl l-[CH2CH20[EO]nH]2
An economical reaction scheme is as follows.
SCHEME 5
Rl OSO3~Na+ + H-N--[(EO)H]2 HEAT ~ Rl N--[(EO)H~2
R--N--[(EO)H]2 + 2 n~ BAHEACTAT~ Rl N--[(EO)(EO)~
Rl N--[(EO)(EO)nH32 + CH3CI ~ Rl I--[(EO)(EO)r~k
CH3 Cl
The following p~ll~,t~ .. s. ize the optional and plefelled reaction conditions of
~ Scll~m~ 5. Step 1 of the reaction is preferably conAl~ct~ in an ;~ Ollc mPAil~m. Reaction
. ~ . ... . . . .
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11
t~l'peldlures are typically in the range of 140-200~C. Reaction ple3sules are 50-1000 psig.
A base catalyst, preferably sodium hydroxide can be used. The mole ratio of l~c~ r~ are
2:1 to 1:1 amine to alkyl sulfate. The reaction is preferably con~ cted using Cg-C14 all~yl
sulfate, sodium salt. The ethoxylation and qudt~ dtion steps are carried out using
5 conventional con~litiQnc and re?,ct~ntc.
Under some cil.-.. ~l;~nres reaction SchPmP 5 results in products which are sllfficipntly
soluble in the a~l~Po--c reaction mPf~ m that gels may form. While the desired product can
be recovered from the gel, an alternate, two-step synthesis .SchPmP 6, hereinafter, may be
10 more desirable in some collull~.~;ial ch~ res. The first step in SchPmP 6 is con~ ctPd
as in .SchPmP 5. The second step (ethoxylation) is preferably con~lllrted using ethylene
oxide and an acid such as HCI which provides the quat~ surfactant. As shown below,
chlorohydrin i.e., chloroell~ol, can also be reacted to give the desired bishydroxyethyl
derivative.
For reaction .SchPrnP 6, the following palalllct .s s~n....~.~e the optional and pn.fe,l.,d
reaction conditions for the first step. The first step is plef, ,dbly con~ ctPd in an aqueous
...P~ .. Reaction t~"ll~,atures are typically in the range of 10~230~C. Reactionp~,S~ S are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react
20 with the HSO4-ge,~,ated during the reaction, or an excess of the amine can be employed to
also react with the acid. The mole ratio of arnine to aLkyl sulfate is typically from 10:1 to
1:1.5; preferably from 5:1 to 1:1.1; more preferably from 2:1 to 1:1. In the product
l'eco~ r step, the desired s~b~ nled amine is simply allowed to se~)alate as a distinct
phase from the ~ qneo~ls reaction mPdillm in which it is insoluble. The second step of the
25 p~cess is co~ cr~ cl under conv..llional reaclion conditions. Further ethoxylation and
uuàte~l~;7~ir~n to provide bis-AQA surf. ~t~n~c are con~ cted under standard reaction
con~ ;on~
.~rhPmP 7 can optionally be co~ cled using ethylene oxide under standard ethoxylation
30 conditions, but ~ill.uul catalyst, to achieve monoethoxylation.
The following illustrates these additional reaction schPmPs~ wherein "EO" le~ ,sc.l~ the
-CH2CH2O- unit. In the reactions, either an inorganic base, an organic base or excess
amine l~ac~ul is used to neutralize generated HSO4.
. . . . . . . . ..... . .
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12
Scheme 6
Rl OSO3Na+ + H,N--CH2CH2-OH ~ Rl N--CH2CH2-OH
I ,CH2CH20H
R--NCH2CH20H + ClCH2CH20H ' RN~
CH2CH20H
Srl-P.nP 7
B ,CH2CH2OH
R N--CH2CH2OH NoCatalyst 'EOnH
The following further illustrates several of the above reactions solely for the
conveniP~ e of the fonmllq~or, but is not intPrl-lPd to be 1;...;~ thereof.
Svnthesis A
~?ar~tion of N.N-Bis(2-hydroxyethYl)dodecylamine
To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles),
14.55 g of ~ .olan~ine (0.1384 moles), 7.6 g of 50 wt. % sodiwn hydroxide solution
(0.095 moles) and 72 g of r1ictill~pd H20. The glass liner is sealed into a 500 ml, stainless
steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 34
15 hours. The llli~Ule iS cooled to room ~ alul~, and the liquid contents of the glass liner
are poured into a 250 ml sel)al,.to.y funnel along with 80 ml of chloroform. The funnel is
shaken well for a few minutes and then the ~ ule is allowed to sepa,ate. The lower
chloluful,.l layer is drained and the chloroform e~a~o.~led off to obtain product.
20 Sy~ esis B
. "al~lioll of N.N-Bis(2-h~loA~ l)dodecylamine
1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the pl~se.lce of
base in the ..~cr described in Synthesis A. The resllltin~ 2-hydroxyethyldodecylamine is
25 r~co~el~d and reacted with l-chloroethanol to pl,~,are the title co..ll,uund.
Synthesis C
ralion of N~N-Bis(2-hydroxyethYl)dodecvlamine
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13
To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles),
21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. ~ sodium hydroxide solution
(0.095 moles) and 72 g of tli.~tillP~ H20. The glass liner is sealed into a 500 mL st~inl~ss
steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 3~
hours. The ll~clul~ is cooled to room le.~ alul~ and the liquid colltenls of the glass liner
are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is
shaken well for a few ~ Jt~s and then allowed llliAIul~ to scp~dLe. The lower chloroform
layer is drained and the chlorofollll is eva~o~àl~d off to obtain product. The product is
10 then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at
120-130~C to produce the desired final product.
The bis-su~liluled amines pl~l,arcd in the Çol~oulg Syntheses can be further ethoxylated
in standard fashion. Quaternization with an alkyl halide to form the bis-AQA surfactants
15 herein is routine.
According to the fol~go.l.~, the following are non~imi~in~, specific illustrations of bis-AQA
surf~rt~nts used herem. It is to be lmdc.~lood that the degree of aLkoxylation noted herein
for the bis-AQA surf~ct~ntc is le~,led as an average, following co~ on practice for
20 conventional ethoxylated nulliOlliC Slll rh~ . TlliS iS because the ethoxylation rcaC~ionS
typically yield llfi~lul~s of materials with differing degrees of ethoxylation. Thus, it is not
unCO-n~un to report total EO values other d~an as whole Illllllbc~ e.g., "E02.5~,
"EO3.5 n .
De~ ................ Rl R2 ApR3 A~qR4
bis-AQA-1 C12-C14 CH3 EO EO
(also ~,f.,,.~ to as
Coco Methyl EO2)
bis-AQA-2 C12-C16 CH3 ~EO~2 EO
bis-AQA-3 C12-C14 CH3 ~EO~2 ~EO~2
(Coco Methyl EO4)
bis-AQA4 C12 CH3 EO EO
bis-AQA-5 C12-C14 CH3 ~EO~2 (EO)3
, ~
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14
bis-AQA-6 C12-C14 CH3 ~EO~2 (EO)3
bis-AQA-7 C8-C 18 CH3 (EO)3 (EO)2
s
bis-AQA-8 C12-C14 CH3 (EO)4 (EO)4
bis-AQA-9 C12-C14 C2H5 (EO)3 (EO)3
bis-AQA-10 C12-C18 C3H7 (EO)3 (EO)4
bis-AQA-ll C12-C18 CH3 (propoxy) (EO)3
bis-AQA-12 Clo~C18 C2H5 (iso-~l~ol)o~-~)2 (EO)3
bis-AQA-13 Clo~C18 CH3 (EO/po~2 (EO)3
bis-AQA-14 Cg-Clg CH3 (E~)15* (EO)l5*
bis-AQA-15 Clo CH3 EO EO
bis-AQA-16 Cg-C12 CH3 EO EO
bis-AQA-17 Cg-Cl l CH3 ~ EO 3.5 Avg. -
bis-AQA-18 Cl2 CH3 - EO 3.5 Avg. -
bis-AQA-l9 Cg- C14 CH3 ~E~~10 (EO)10
bis-AQA-20 Clo C2H5 ~EO~2 (EO)3
bis-AQA-21 C12-C14 C2H5 (EO)5 (EO)3
bis-AQA-22 C12~C18 C3H7 Bu (EO)2
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*Ethoxy, optionally end-capped with methyl or ethyl.
Highly plefell~d bis-AQA compounds for use herein are of the formula;
Rl /CH2CH2OH
N ~ X~
CH3/ CH2CH2OH
wherein Rl is Cg-Clg hydrocarbyl and mi~Llul s thereof, preferably Cg, Clo, C12, C14
aLkyl and lllLl~lules thereof. X is any convenient anion to provide charge balance,
preferably chloride. With lefe..,nce to the general bis-AQA s~luclule noted above, since in
10 a ~-. fe.led compound Rl is derived from coconut (C12-C14 alkyl) fraction fatty acids, R2
is methyl and ApR3 and A'qR4 are each monoethoxy, this pl~fc~led type of co,ll~u~d is
ref.,...,d to herein as "CocoMeEO2" or "bis-AQA-l" in the above list.
Other bis-AQA ~UI fi.~ useful herein include coml~oullds of the formula:
R~ +~(CH2CH2O)pH
R2/ \(CH2CH20)qH
whc~h~ Rl is Cg-Clg hy~oca.b~l, preferably Cg-C14 al}cyl, independently p is 1 to 3 and
q is 1 to 3, R2 is Cl-C3 aLtcyl, p~,f, ,ably methyl, and X is an anion, especi~lly chloride or
20 blollude.
Other co..~ s of the folcgolng type include those ~he,e~ the ethoxy (CH2CH20) units
(EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and [CH2CH(CH30] units(i-Pr) or n-propoxy units (Pr), or I~ ules of EO andlor Pr and/or i-Pr units.
A highly piefe.l~d bis-AQA col~l~wld for use in under built formulations are of the
formula wherein p andlor q are integers in the range of bel~.~,.,n 10 and 15. This
compound is particularly useful in laundry handwash de~lgelll compositions.
30 Non-AOA Detersive Sul ri.. ,;.."~
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16
In addition to the bis-AQA surfactant, the compositions of the present invention preferably
further comprise a non-AQA surfactant. Non-AQA surf~rt-q-nts may include essentially any
anionic, nonionic or additional cationic surfactant.
s
Anionic Su.r~ctant
Nonlimiti~ exarnples of anionic ~.ulr;~ , useful herein typically at levels from 1% to
55%, by weight, include the conventional C11-C1g alkyl benzene sulronahs ("LAS") and
10 plilll~y ("AS"), branched-chain and random Clo-C20 alkyl sl~lfq-tes, the Clo-C1g
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 illhge. . of at least 7, plefel~ly
at least 9, and M is a water-solubilizing cation, especiqlly so~ m, u~.alulated s-llfqtPs such
as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the C1o-C18 slllf~
15 polyglycosides, the Clo-C1g alkyl alkoxy s~llfq-t~s (nAEXSn; especiqlly EO 1-7 ethoxy
sl~lfqtes), and the Clo-C18 aL~cyl aLkoxy carboxylates (especiqlly the EO 1-5
ethoxycarboxylates). The C12-Clg betaines and sulfobet-q-in~s ("s~lt~in~s"), Clo-C~8
amine oxides, can also be inrll~ded in the overall compositions. Clo-C20 conventional
soaps may also be used. If high su~lsin~ is desired, the branched-chain Clo-C16 soaps may
20 be used. Other conventional useful ~.ul r;~ are listed in standard texts.
Nonionic Surfartq.~ltc
Nonlimitin~ examples of nonionic surf-q-ct~ntc useful herein typically at levels from 1% to
25 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy
fatty acid amides (PFAA's), aL~cyl polyglycosides (APG's), C1o-C1g glycerol ethers.
More "~ jfi~lly, the con~l~n~qtiQn products of primary and secondary ~lirh~tir alcohols
with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the llOlllOnlC
30 surfactant in the present hl~elllio.l. The aL~cyl chain of the alirh-q-tir alcohol can either be
straight or b~ rh~d, primary or secondary, and generally contains &om 8 to 22 carbon
atoms. P~l,fel.~,d are the conrl~ncation products of alcohols having an alkyl group
cont-q-ini~ from 8 to 20 carbon atoms, more preferably &om 10 tol8 carbon atoms, with
&om 1 tolO moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of
35 alcohol. Examples of co-n-ll.,.;ially available nonionic surfact-q-ntc of this type include:
CA 02255005 1998-ll-17
WO 97/43394 PCT/US97/0844
17
TergitolTM 15-S-9 (the con~encqtion product of Cll-Cls linear alcohol with 9 moles
ethylene oxide) and TergitolTM 24-L-6 NMW (the con-l~nC~ion product of C12-C14
prirnary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution),
both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product
of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the
conrl~ncqtion product of C12-C13 linear alcohol with 3 moles of ethylene oxide),NeodolTM 45-7 (the co~ ;on product of C14-Cls linear alcohol with 7 moles of
ethylene oxide) and NeodolTM 45-5 (the co~ t~;on product of C14-C1s linear alcohol
with 5 moles of ethylene oxide) 1~l eled by Shell ChPmicq-l Compqny; KyroTM EOB (the
10 con~lencq-tion product of C13-C1s alcohol with 9 moles ethylene oxide), In~l~eled by The
Procter & Gamble Colnl)any; and Genapol LA 030 or 050 (the con-lencqtion product of
C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The ~ref~ ~cd
range of HLB in these AE nonionic sulra~;lants is from 8-11 and most preferred from 8-10.
Con-l~nc-q-t~s with propylene oxide and butylene oxides rnay also be used.
Another class of p,efe.l~d nol~ionic ~ulr~ t~ for use herein are the polyhydroxy fatty
acid amide surfactants of the formula.
R2--C~ Z
O R
wherein R1 is H, or C14 I.~dloc~byl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture
thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear
l~ydlocdlt"rl chain with at least 3 hydroxyls directly co....~clr~l to the chain, or an
aLkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C11 1s alkyl or
25 Cls 17 alkyl or aL~enyl chain such as coconut aL~cyl or nuxtures thereof, and ~ is derived
from a re~ c;-~g sugar such as gll~cose, fructose, mqltose, lactose, in a reductive qminqtion
reaction. Typical examples include the C12-Clg and C12-C14 N-methylglllcqmidec. See
U.S. 5,194,639 and 5,298,636. N-aL~coxy polyhydroxy fatty acid amides can also be used;
see U.S. 5,489,393.
Also useful as the nonionic ~ulr~c~nt in the present invention are the alkylpolysaccharides
such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986,
having a hydrophobic group contqining from 6 to 30 carbon atoms, preferably from 10 to
16 carbon atoms, and a poly~accha~ide, e.g. a polyglycoside, hydrophilic group contqining
, .. . .. . .. .
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18
from 1.3 to 10, preferably from 1.3 to 3, most preferably &om 1.3 to 2.7 saccharide units.
Any reducing saccharide cont~inin~ 5 or 6 carbon atoms can be used, e.g., glucose,
galactose and g~lqrtosyl moieties can be substituted for the glucosyl moieties (optionally
the hydrophobic group is artqrhPd at the 2-, 3-, 4-, etc. positions thus giving a glucose or
5 galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g.,
bc~ eell the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-
positions on the prece~ g saccharide units.
The l,refellcd aL~cylpolyglycosides have the formula:
R20(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group con~;cl;ng of alkyl, alkylphenyl, hydroxyalkyl,
hydroxyalk~l~h~nyl, and lllib~ les thereof in which the alkyl groups contain from 10 to 18,
plcr lably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10,
preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3
to 2.7. The glycosyl is preferably derived from glucose. To pr~,~are these col~o~lnds, th
alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a
source of glucose, to form the glucoside (att~ at the l-position). The a~ itionql
20 glycosyl units can then be qtt~ Pd between their 1-position and the prece~line glycosyl
units 2-, 3-, 4- and/or 6-position, preferably pre~ominqtely the 2-position.
Polyethylene, polypropylene, . nd polybutylene oxide con~ C~t~s of alkyl phenols are also
suitable for use as the ~ ;onir, surfactant of the surfactant systems of the present invention,
25 with the polyethylene oxide con~ C~t~s being pl~fe.led. These compounds include the
co~ nc~irJn products of alkyl phenols having an alkyl group contqining from 6 to 14
carbon atoms, pl~,f~"ably from 8 to 14 carbon atoms, in either a straight-chain or
bl~ched~hain configuration with the aIkylene oxide. In a pref~.l.,d embo~limPnt, the
ethylene oxide is present in an Z~ O~ t equal to from 2 to 25 moles, more preferably from 3
30 tol5 moles, of ethylene oxide per mole of alkyl phenol. Co.lllllel~eially available nonionic
surf~t~ntc of this type include IgepalTM CO-630, ll~rl~eted by the GAF Corporation; and
TritonTM X~5, X-114, X-100 and X-102, all marketed by the ~ohm & Haas Company.
These surfactants are conllllonly referred to as alkylphenol aL~coxylates (e.g., alkyl phenol
ethoxylates).
CA 02255005 1998-11-17
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19
The con~ncation products of ethy}ene oxide with a hydrophobic base formed by thecondensation of propylene oxide with propylene glycol are also suitable for use as the
additional nonionic surfactant in the present invention. The hydrophobic portion of these
compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit
5 water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion
tends to increase the water solubility of the molecule as a whole, and the liquid chal~cL~r of
the product is retained up to the point where the polyoxyethylene content is 50% of the
total weight of the co.~ ca~ion product, which cG...,sponds to co~ nC~Iion with up to 40
moles of ethylene oxide. Examples of compounds of this type include certain of the
0 co~ frcially-available PluronicTM surf~ctantc, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic ~.nr~ system of the
present invention, are the con~nC~tion products of ethylene oxide with the product
resultin from the reaction of propylene oxide and ethylen~~ ;ne. The hydrophobic15 moiety of these products cor~ of the reaction product of ethylen~li~ r and excess
propylene oxide, and generally has a molecular weight of from 2500 to 3000. Thishydrophobic moiety is co~ nced with ethylene oxide to the extent that the co~-del.r-l;ol-
product contains from 40% to 80% by weight of polyoxyethylene and has a molecular
weight of from 5,000 to 11,000. Examples of this type of nonionic ~u~ ra~ include
20 certain of the con~,crcially available TetronicTM compounds, marketed by BASF.
Additional Cationic surfactants
Suitable cationic surf~ ntc are preferably water dis~l~il,lc compound having ~u~raclant
25 plo~,lies CGIl~ iSil~g at kast one ester (ie -COO-) linkage and at least one cationically
ch~gc~ group.
Other suh~J- c~tinnir surf~ct~ntc include the quate,~y ~ onillm surf~t~ntc selected
from mono C6-C16, preferably C6-Clo N-aL~yl or aL~cenyl al~ lOlliUIII surfaetantc whcle
30 the re~n~ining N positions are SU~G5~ ~ by methyl, hydroxyethyl or hydroxypropyl
groups. Other suitable cationic ester ~ulr;~ I;tntc, inrhldjng choline ester surfarr~ntc~ have
for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
Optional Dete.~el,l In~redients
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WO 97/43394 PCT/US97/08445
The following illustrates various other optional ingredients which may be used in the
compositions of this invention, but is not intended to be limi~ing tnereof.
Additional Bleach
The dete.gent comrositions herein rnay optionally comprise an additional ble~ching agent.
When present, such additional bleqching agents will typically be at levels of from 1% to
30%, more typically from 5% to 20%, of the dctelge.lt co.llposilion, especiqlly for fabric
lq-l-n-l~ring.
The bk,~hin~ agents used herein can be any of the bl~hi.-g agents useful for det~,.~.ll
compositions in textile cleqni~ hard surface cleaning, or other cle-q-ning purposes that are
now known or becolllc known. These include oxygen bleaches as well as other ble~,chin~
agents. ~.l,uiate bleachcs, e.g., sodium pe.l,o~ c (e.g., mono- or tetra-hydrate) can be
used herein.
AL~ali metal or aL~ali earth metal pe.~arl,ondtcs, particularly sodium ~lc~lJollate are
pl~.fi ~led percarl,o.~tes for inclusion in compositions in accordalKe with the invention.
Sodium ~rcall~nate is an addition compound having a formula coll. s~nding to
2Na2C03.3H202, and is available collllll~.~;ially as a crystalline solid. Colllllle.cial
suppliers include Solvay, PMC, Tokai Denka and others.
A pler~lcd ~ l~t~, bleach co.ll~lises dry particles having an average particle size in
the range from 0.5 mm to 1 mm, not more than lO~ by weight of said particles being
smaller than 0.2 mm and not more than 10% by weight of said particles being larger than
1.250 mm.
The ~.~l,ollat~ is most plef. .ably incorporated into such compositions in a coated form
which provides in-produ~l stability.
A suitable coating material providing in product stability C~ liScS mixed salt of a water
soluble alkali metal slllphqt~ and carbonate. Such coatings together with coating processes
have previously been desc,ibed in GB-1,466,799, granted to Interox on 9th March 1977.
The weight ratio of the mixed salt coating material to ~I~ ~nate lies in the range from 1
: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1: 49 to 1:
19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has tne
, .... . . . .
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21
general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to
1.0 and most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric acids or other
5 h1o~g~lics), waxes, oils, fatty soaps can also be used advantageously within the present
invention
Another categol y of ble~ching agent that can be used without l~,;,lriCliOn enco...p~ses
~icarl,oxylic acid ble~rhin~ agents and salts thereof. Suitable examples of this class of
10 agents include m~gnPsil-m Illon~loxyphthql-q-te hexahydrate, the mq~ sill~ll salt of meta-
chloro pe.b~,nzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydo~ecqn~-lioic
acid. Such ble~qching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued
Nov~mber 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985,
European Patent Appli~qtion 0,133,354, Banks et al, published reb,udly 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued Nove~.ber 1, 1983. Highly plef~ ed
blearl-in~ agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
Peroxygen bleac~ agents can also h,e used. Suitable peroxygen ble~ching coll.~unds
20 include sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Perborate bleach, persulfate bleach (e.g., OXONE, m~nllf~t~tured co.lllllercially by
DuPont) can also be used.
Mixtures of bleac~ agents can also be used.
Bleach Activators
Bleach activators are ylcf~ ~lcd components of the composition where a peroxygen bleach is
present. If present, the ~ n~ of bleach activators will typically be from 0.1 % to 60%,
30 more typically from 0.5% to 40% of the ble~.rhing composition collly~ g the bl~l~hi.~g
agent-plus-bleach activator.
The combination of peroxygen blenclling agents and bleach activators results in the in situ
production in aqueous solution (i.e., during the washing process) of the peroxy acid
35 collc;,l,ol~ding to the bleach aclivdlor. Various nonlimiting examples of activators are
. ,, .~.
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WO 97143394 PCT/US97/08445
22
disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The nonanoyloxyl~llzc"c sulfonate (NOBS) and tetraacetyl ethylene ~ min~
(TAED) activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,551 for other typical bleaches and activators useful herein.
Highly plefe,-cd amido-derived bleach activators are those of the formulae:
R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L
10 wl~ Rl is an alkyl group corlt~ining from 6 tol2 carbon atoms, R2 is an alkylene
co~ g from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl cont~ining from 1
to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that
is displaced from the bleach activator as a con~eqllenre of the nucleophilic attack on the
bleach activator by the perhydrolysis anion. A prer.,.led leaving group is phenyl sulfonate.
~ef~ll.,d examples of bleach activators of the above formulae include (6-oc~ Q-
caproyl)o~ylA ,~ f~ fonate, (6-n~ Qcaproyl)oxyb.n,- ~rs~lfonate, (6~ o-
caproyl)oxyb~n~ a~lfonate, and n~lules thereof as described in U.S. Patent 4,634,551,
incorporated herein by rer~ce.
Another class of bleach a~;livato.~ colll~lises the benzoxazin-type activators disclosed by
Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by
r~,f~,~e.lce. A highly l"efelled activator of the benzoxazin-type is:
~N~C~
Still another class of pfefel.ed bleach activators includes the acyl lactam activators,
especi~lly acyl caprolactarns and acyl valerolactams of the formulae:
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WO 97/43394 PCT/US97/08445
23
O C--CH2--CH2
C H2--C H2
R--C--N~
CH2--CH2
S ~hele.n R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group con~ining from 1 to 12
carbon atoms. Highly p.ef~ d lactam activators include benzoyl caprolactam, octanoyl
caprolactam, 3,5,5~ hyll~x~noyl caprolactam, nonanoyl caprolact~m, decanoyl
caprolac~m, ..,--lece.~yl caprolact~m, benzoyl valerolactam, octanoyl valerolactarn,
decanoyl valero!act~m, ~ Pcenoyl valerol;~ct~m"lol~loyl valerolactam, 3,5,5-
hil~ Lhylh ~noyl valerolactamand Il~ r~s thereof. Seealso U.S. Patent4,545,784,
issued to Sanderson, October 8, 1985, incorporated herein by ~,f; ,e~ce, which discloses
acyl caprolactams, including benzoyl caprol~rt~m, adsorbed into sodium perborate.
Bleach Catalyst
Bleach catalysts are ~lefe.led components of colllposilions of the present invention that, in
addition to the photobleach, comprise an oxygen rel~c;--~ bleaching agent. Bleach
catalysts are well known in the art and include, for example, the m~ se-based catalysts
lose~l 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 Eulo~ Pat. App. Pub. Nos. 549,271Al, 549,272Al, 544,440A2, and
544,490A1; ~,fe~.ed ~les of these catalysts include MnIV2(u-O)3(1,4,7~ hyl-
1 ,4,7-L,i~acyclo~onane)2(PF6)2, Mnm2(u-O)l(u-OAc)2(1,4,7-~ thyl-1 ,4,7-triazacyclo-
nonane)2 (C104)2, MnIV4(u-0)6(1,4,7-tri~7~cyclononane)4(CI04)4, MnmMnIV4(u-
O)l(u-OAc)2 (1,4,7-~ le~llyl-1,4,7-triazacyclonollane)2(Cl04)3, MnIV(1,4,7-L~.,IIeLhyl-
1,4,7-triazacyclol.o.~ )- (OCH3)3(PF6), and mixtures thereof. Othermetal-basedbleach
catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use
of .~n~ se with various complex ligands to enhance ble~rl ing 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.
CA 022SS00S 1998-11-17
WO 97/43394 PCT/US97/08445
24
As a practical matter, and not by way of limitation, the co~ )osilions 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 ~qtleOl~ washing liquor, and will preferably provide from 0.1
ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in the
laundry liquor.
Cobalt bleach catalysts useful herein are known, and are desc.ibed, for example, in M. L.
Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inor~. Bioinor~. Mech.,
10 (1983), 2, pages 1-94. The most plef~ d cobalt catalyst useful herein are cobalt
pent~qmin~ acetate salts having the formula [Co(NH3)sOAc] Ty~ wL~ "OAc~
es~ an acetate moiety and "Tyl' is an anion, and especi~lly cobalt pent~ acetatechloride, [Co(NH3)sOAc]C12; as well as [Co(NH3)sOAc](OAc)2;
[C~(NH3)5OAc](pF6)2; [Co(NH3)sOAC](sO4); [Co(NH3)sOAc](BF4)2; and
15 [Co(NH3)sOAc](NO3)2 (herein "PAC~).
These cobalt catalysts are readily plcpar~,d by known p,ocedules, such as taught for
example in the Tobe article and the rcfefe,~ces cited therein, in U.S. Patent 4,810,410, to
Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis
20 and Chdldc~1izdlion of IllOlganiC Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-
3; Inor,e. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982); Inor~.
Chem.. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical
Ch.,ulisllY, 56, 22-25 (1952).
25 As a pld.;lical matter, and not by way of limit~tion, the automatic dishwashing
col,.~osilions and cle~ P plocesses herein can be adjusted to provide on the order of at
least one part per hundred million of the active bleach catalyst species in the aqueous
washing ...Pd; ~.., and will preferably provide from 0.01 ppm to 25 ppm, more preferably
from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach
30 catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an
auluu~dtic dishwashing process, typical d~llUllldliC dishwashing compositions herein will
col~ ise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach
catalyst, especi~lly ~ AI~se or cobalt catalysts, by weight of the cleaning compositions.
35 Builders
CA 022SSOOS 1998-11-17
WO 97/43394 PCT/US97/08445
Detelge"l builders can optionally but preferably be included in the compositions herein, for
example ~o assist in controlling mineral, especially Ca and/or Mg, hardness in wash water
or to assist in the removal of particulate soils from surfaces. Builders can operate via a
5 variety of mPrhqni~mc inr!l-~iing forming soluble or insoluble complexes with hardness
ions, by ion el~ch~n~e, and by ol~.hlg a surface more favorable to the precipitation of
ha~ ess ions than are the surfaces of articles to be cleaned. Builder level can vary widely
d~ending upon end use and physical form of the CG~ oSilion. Built det. Ige.,~. typically
Co~ iSC at least 1% builder. Liquid forrm~l~tirJns typically comprise 5% to 50%, more
10 typically 5% to 35% of builder. Granular formulations typically colll~lise from 10% to
80%, more typically 15% to 50% builder by we}ght of the del~lge.ll composition. Lower
or higher levels of builders are not PYrluderl. For example, certain detelgelll additive or
high-surfactant form~ tions can be llnbuilt.
15 Suitable builders herein can be sekc~ d from the group co~cictin~ of ~ho~hates and
polypho~h~l~s, esppc~ y the sodium salts; silir~t~Ps inrlu~i~ water-soluble and hydrous
solid types and in~ ling those having chain-, layer-, or three~impncion~l- structure as
well as ~llol~/hous-solid or non-stluctured-liquid types; call,o,~tes, bic~l,o,lates,
s~s~ ira~ l,onates and c~l~llalt: minerals other than sodium calbOI~ or ses~ .l,o,~le;
20 ~ silir~tPs; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble
no~ulrac~ll carboxylates in acid, sodium, pot~csillrn or aL~canolammonium salt form, as
well as oligonlc,lic or water-soluble low molecular weight polymer carboxylates inrluAi
aliphatic and aromatic types; and phytic acid. These may be compl~ Pd by borates,
e.g., for pH-burf~"ing ~ull~oses, or by sl~lf~t~Ps, especially sodium sulfate and any other
25 fillers or carriers which may be h"~l~l to the engil-~ .,ng of stable surfactant and/or
builder-co..~ g det~l~enl co.~ ilions.
Builder ~ S, s.-...- t;...Ps termed "builder systems" can be used and typically col..l..ise
two or more conventional builders, optionally complem~tPd by chPI~ntc, pH-buffers or
30 fillers, though these latter materials are generally ~cco~ ed for sepalately when describing
q~z~ s of materials herein. In terrns of relative qu~ntitips of surfactant and builder in
the present d~ genLs, p~fe,l.,d builder systems are typically forTn~ ted at a weight ratio
of surfactant to builder of from 60:1 to 1:80. Certain prcf.,l,ed laundry dc;Lerge"l~ have
said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1Ø
CA 02255005 1998-11-17
WO 97/43394 PCT/US97/08445
26
P-cont~ining dete~ge~ll builders often preferred where permitted by legislation include, but
are not limited to, the alkali metal, a~ oluum and alkanolammonium salts of
polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric
meta-phosphates; and phosphonates.
Suitable silicate builders include alkali metal .cilirqtPs, particularly those liquids and solids
having a SiO2:Na2O ratio in the range 1.6: 1 to 3.2: 1, inrlu.ling, particularly for automatic
dish~ashil g purposes, solid hydrous 2-ratio silir-q-tPs ~lal~ted by PQ Corp. under the
tra~k~ f BRITESIL~, e.g., BRITESIL H20; and layered silir-q-~es, e.g., those desclibcd
in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, so.. ~t;.. ~s abbreviated "SKS-
6", is a crystalline layered qlltrninillm-free ~-Na2SiOs morphology silicate marketed by
Hoechst and is preferred especiqlly in granular laundry compositions. See ple~a,dli~re
m~th~s in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such
as those having the general formula NaMSixO2x+ 1 YH2O wherein M is sodium or
l~y-lrogen, x is a ,.~llber from 1.9 to 4, preferably 2, and y is a number from 0 to 20,
preferably 0, can also or alternately be used herein. Layered silir~tPs from Hoechst also
include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ~ and y layer-silicate forms. Other
silicates may also be useful, such as l--a~ ... silicate, which can serve as a c.;~ g
agent in granules, as a stabilising agent for bleaches, and as a component of suds control
systems.
Also suitable for use herein are ~ c; -,d crystalline ion exchqnge materials or hydrates
thereof having chain ~L~u~lur~, and a cou.~o,ilion ~ ese.lled by the following general
formula in an anhydride form: xM20 ySiO2.zM'O wlle~ M is Na and/or K, M' is Ca
and/or Mg; ylx is 0.5 to 2.0 and ztx is 0.005 to 1.0 as taught in U.S. 5,427,711,
Sakaguchi et al, June 27, 1995.
Suitable calbo~L~ builders include ~ lin~ earth and aLkali metal c~ll,ol~tes as disclosed
in German Patent Applir~tion No. 2,321,001 published on November 15, 1973, ~Itho~lgh
sodium bica,l~l~a~e, sodium carbonate, sodium sesquicalbo~Le, and other carbonate
minerals such as trona or any convenient multiple salts of sodium c~bG.~te and c~lcinm
c~l,onate such as those having the co"ll)osition 2Na2C03.CaC03 when anhydrous, and
even calcium c~l,onates inrl~l~ling calcite, aragonite and vaterite, especially forms having
high surface areas relative to co--li)act calcite may be useful, for example as seeds or for
use in synthetic dete.ge.lt bars.
CA 022SSOOS 1998-11-17
WO 97143394 PCT/US97/08445
27
Aluminosilicate builders are especially useful in granular detergents, but can also be
incol~,uldted in liquids, pastes or gels. Suitable for the present purposes are those having
empirical formula: [MZ(Alo2)z(sio2)v] xH2O wl.c.~in z and v are integers of at least 6,
S the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
~lmninosilicates can be crystalline or amorphous, naturally-ocwlli,~g or syn~h~tirqlly
derived. An al~ osil~cate production m~thod is in U.S. 3,985,669, Krummel, et al,
October 12, 1976. ~f~_.led ~ lh.lic crystalline all~..i..ns;li~ate ion exchq~e materials
are available as Zeolite A, Zeolite P (B), Zeolite X and, to ~hat~,ve. extent this differs
10 from Zeolite P, the so-called Zeolite MAP. Natural types, inrll~lin~ clinoptilolite, may be
used. Zeolite A has the formula: Na12[(AlO2)12(SiO2)12] xH2O wherein x is from 20 to
30, especiqlly 27. Dehydrated zeolites (x = O - 10) may also be used. Preferably, the
q.~ nnsilirqte has a particle size of 0.1-10 lllicrolls in ~ trl .
15 Suitable organic d~,t_-~gent builders include polycarboxylate colll~ul~ds, in~ water-
soluble l~o,~ulr~ctant dica,lo~ylates and tricarboxylates. More typically builder
polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
Carboxylate builders can be forrm~ e~ in acid, partially neutral, neutral or ovelbascd
form. When in salt form, alkali metals, such as so~ m, ~!-~CS; ~ , and Ihhil~m, or
20 aL~canolanùllo~i~ll salts are plefi,.l~d. Polycarboxylate builders include the ether
polycarboxylates, such as oxycli~-~cc;nz~e, see Berg, U.S. 3,128,287, April 7, 1964, and
i et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S.
4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and
alicyclic colll~uilds, such as those described in U.S. Patents 3,923,679; 3,835,163;
2S 4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether h~dl~ypolycarboxylates, copolymers of maleic
anhydride with ~ ",e or vinyl methyl ether; 1, 3, S-kihydroxy 'Ge.~.le-2, 4, 6-
trisulphonic acid; carboAy~ yloxysuccinic acid; the various alkali metal, allul~o~ m and
~.ub~.l;U~ .. O~ .. salts of polyacetic acids such as ethyl~-P~iiz~.. inf tetraacetic acid and
nitriloLIiace~ic acid; as well as mellitic acid, succinic acid, polymaleic acid, ben~ene 1,3,5-
~lic~ul,o~ylic acid, ca,boAy~ loxysuccinic acid, and soluble salts thereof.
Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g.,
35 for heavy duty liquid dc~lgell~., due to availability from renewable resources and
CA 02255005 1998-11-17
WO 97143394 PCT/US97/08445
28
biodegradability. Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicates. Oxydisuccinates are also especially
useful in such compositions and combinations.
Where pe.l~ ed, and especially in the formulation of bars used for hand-laundering
operations, alkali metal pho~l,hates such as sodium tripol~yhos~hat~s, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as
ethane-l-hydroxy-1,1-dipho~l.honate and other known phosphonates, e.g., those of U.S.
3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have
10 desirable anticcq1ing ~lo~lies.
Certain detersive surfartantc or their short-chain homologs also have a builder action. For
u~ biguous formula ilCCO~ oses, when they have surfactant capability, these
,l~t~,.ials are ~ d up as detersive surfactants. I~efe,.ed types for builder functionality
15 are illustrated by: 3,3-dicarboxy4-oxa-1,6-h~YanPAio~tes and the related co~ lds
disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the
Cs-C20 alkyl and alkenyl sl~ccini~ acids and salts thereof. Succinate builders also include:
laurylsuccinate, myristyl~.,cc;..~l~, palmitylsuccinate, 2~odecenylcllccin~t~ (pler.,lle~), 2-
pent dec~nylsuccinate. Lauryl-succ~ . s are described in European Patent Application
86200690.5/0,200,263, published Nov~,,n~l 5, 1986. Fatty acids, e.g., C12-C1g
monocalboxylic acids, can also be incorporated into the colnposi~ions as surfactant/builder
materials alone or in combination with the afof~ oned builders, especially citrate
and/or the s~lccinqtç builders, to provide additional builder activity. Other suitable
polycarboxylates are ~icclosed in U.S. 4,144,226, Cmtchfiel~ et al, March 13, 1979 and in
U.S. 3,308,067, Diehl, March7, 1967. See also Diehl, U.S. 3,723,322.
Other types of inolgao~c builder materials which can be used have the formula (MX)i Cay
(CO3)z ~.h~ ,~ x and i are i~tegels from 1 to 15, y is an integer from 1 to 10, z is an
integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the
30 equation ~i = l 1s(xi multiplied by the valence of Mi) + 2y = 2z is 5qticfi~1 such that the
formula has a neutral or '~bqlqnredll charge. These builders are referred to herein as
"Mineral Builders". Waters of hydration or anions other than carbonate may be added
provided that the overall charge is balqn~ed or neutral. The charge or valence effects of
such anions should be added to the right side of the above equation. ~lably, there is
35 present a water-soluble cation selected from the group concicting of hydrogen, water-
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WO 97/43394 PCT/US97/08445
29
soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more
preferably, sodium, potassium, hydrogen, lithillm, ammonium and mixtures thereof,
sodium and potassium being highly pl.,fell~d. Nonlimiting examples of noncarbonate
anions include those selected from the group co~ g of chloride, sulfate, fluoride,
5 oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and uu~lul.,S thereof.
~,fell~ d builders of this type in their simplest forms are sel~t~ d from the group
conci~ g of Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03)2,
NaKCa2(C03)3, K2Ca2(C03)3, and conlbinations thereof. An çspçci~lly p~f~ d
material for the builder described herein is Na2Ca(C03)2 in any of its crystalline
10 mo~1iflc~tions. Suitable builders of the above-defined type are further illustrated by, and
include, the natural or syl~ ic forms of any one or combinations of the following
minerals: Af~ e, Andcljonile, AshcroftineY, Beyerite, Bol~;~i~, Burbankite,
R~ltcchliite, Caml,llile, Calboc.,.u~ite, Carletonite, Davyne, Dol~ndyi~Y, Fairchildite,
F."li~ e, rl~-7i.~ , (J~defroyite, Gaylussite, Girvasite, Gregolyile, Jouravskite,
15 Kaml,haugiteY, Kc~L~.ile, Kh~nnPchit~ ol~ ,Gd, Liottite, MckelveyiteY,
Microsoll~.lile, Mroseite, Natrofairchildite, Nye.~r~ite, R~ Ce, Sacrofanite,
Schrocki.-ge.ile, Shortite, Surite, Tunisite, Tl~sc~nite, Tyrolite, Vishnevite, and Zemkorite.
~.,f~ d mineral forms include Nye.e.ile, Fairchildite and Shortite.
20 Enzvmes
El~l,les can be inrhl-le.~ in the present det~,rgenl co.ul)osilions for a variety of l,lJl~ses,
inrhl<~ing removal of protein-based, carbo~ ~c-based, or triglyceride-based stains from
~ub~llate-s, for the prevention of refugee dye ~ Ç.,r in fabric laundering, and for fabric
25 l ,i,lo.alion. Suitable ~",es include ~ lut,ases, amylases, lipases, cellulases, peroxidases,
and l~lu.cs thereof of any suitable origin, such as vegetable, animal, baclelial, fungal and
yeast origin. R.,fe,l~,d selecliol~s are i..~ red by factors such as pH-activity and/or
stability optima, th- ~...osl~bility, and stability to active det~lge,lls, builders. In this respect
bac~.ial or fungal elL~ Rs are ~l~r~.l~, such as bacl~,lial amylases and pluteases, and
30 fungal cel~ ces.
"Detersive enzyme~, as used herein, means any enzyme having a cle~ning, stain removing
or ollle.v~ise beneficial effect in a laundry, hard surface cle~ning or personal care dete.~n~
composition. ~er.ll~,d detersive enzymes are hydrolases such as pro~eases, amylases and
35 lipases. P~,fell~d enzymes for laundry purposes include, but are not limited to, proteases,
CA 02255005 1998-11-17
WO 97/43394 PCT/US97/08445
cf~ U~s, lipases and peroxidases. Highly l.lefe~ d for automatic dishwashing areamylases and/or proteases.
Enzymes are normally hlcGl~ated into de-t~ t or dete.gf ~ll additive compositions at
5 levels sufficient to provide a "cle~ni~-effective amo~nt~. The term "clf~nil~ effective
~mount" refers to any amount capable of producing a cl~ning, stain removal, soi~ removal,
wl.it~ g, deodoli~i~, or frechn~oss improving effect on ~ dt~s such as fabrics,
di;~h~ àle. In l,ldclical terms for current cc.ll~l~c.cial p..,palalions, typical sllwul1~s are up
to 5 mg by weight, more typically 0.01 mg to 3 mg, of active c~,l,e per gram of the
10 det~.gf nt composition. Stated oth.,. wise, the compositions herein will typically co,llp.ise
from 0.001% to 5%, preferably 0.01%-1% by weight of a col~llc..;ial e~y.l.e
,l. pa,alio~ t,_ase e.~u~cs are usually present in such co~ ~ial ~ alations at
levels s~lrr~ie-~l to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of
culll~osilion. For certain d.,~.ge.lt~, such as in alllulllalic dish.. asl~ing, it may be desi.a~le
15 to incl~âse the active e~c content of the co~ .f~..;ial preparation in order to ~ f
the total ~ nt of non-catalytically active materials and thereby improve spotting/filming
or other end-results. Higher active levels may also be desirable in highly conce.ll,,.ted
d~,t,.~e.ll formulations.
20 Suitable examples of proteases are the subtilisins which are obtained from particular strains
of B. s~btilis and B. Iic/.~,.iro",.is. One suitable protease is obtau~ed from a strain of
Rg~ , having .~ - . activity thro~ ghol)t the pH range of 8-12, developed and sold as
ESPERASE~ by Novo ~ if S A/S of De,~ , hereinafter NNovo". The p~p~alion of
this e~rll,e and analogous e es is described in GB 1,243,784 to Novo. Other suitable
25 p~Dt~,ases include ALCALASE~ and SAVINASE~ from Novo and MAXATASE~ from
Intc...-lio~ Bio-S~ .- l;cs~ Inc., The NelL.,.lands; as well as E~ut~,asc A as disclosed in
EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28,
1987 and EP 130,756 A, January 9, 1985. See also a high pH ~lotedse from R ~ ilh-~ sp.
NCIMB 40338 dcselibet in WO 9318140 A to Novo. Enzymatic dct,.gen~ conlpli~ g
30 protease, one or more other c.~llles, and a reversible protease ~nhibilOl are desclibed in
WO 9203529 A to Novo. Other plefe~led proteases include those of WO 9510591 A toProcter & l'~mhle . When desired, a protease having decreased adsorption and incleased
hydrolysis is available as des~lil,cd in WO 9507791 to Procter & Gamble. A l~combinaut
trypsin-like plut~ase for d~,t.,.~e.l~ suitable herein is described in WO 9425583 to Novo.
CA 02255005 1998-11-17
W O 97/43394 PCTrUS97/08445
31
In more detail, an especially p~cfe~l~d protease, referred to as "Protease D" is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is derived
from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of
amino acid residues at a position in said carbonyl hydrolase equivalent to po~iLioll +76,
S preferably also in co~ inalion with one or more amino acid residue positions equivalent to
those select~P~ from the group con.~ g of +99, +101, +103, +104, +107, +123,
+27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +204, +206,
+210, +216, +217, +218, +222, +260, +265, and/or +274 accolding to the
llulllbe~ing of R(7ri(lr~ anryloliquefaciens subtilisin, as des~lil~d in the patent applications
10 of A. Baeck, et al, entitled "Protease-Contqining Cleaning Col.lposilions" having US Serial
No. 08/322,676, and C. Ghosh, et al, "BlParh;~ Co.-~ ions Co~ lisillg ~o~ ce
Enzynnes" having US Serial No. 08/322,677, both filed October 13, 1994.
Amylases suitable herein, especjqlly for, but not limited to ~ on,~l;r dishwashing
15 ~ul~oses~ include, for e~al~plc, a-amylases described in GB 1,296,839 to Novo;
RAPIDASE~, Ll~...-l;orlql Bio-Sy.lll.- t;~s, Inc. and TERMAMYL~, Novo.
FUNGAMYL~ from Novo is especiqlly useful. F.-.gi.-~ . ing of enzymes for hllplu~.d
stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985, pp.6518-6521. Certain plefe.l~d embc~i~..f nl~ of the present
20 CGIlll~oSiLions can make use of amylases having improved stability in dete.gc.lLs such as
aulumalic dishwashing types, especiqlly improved oxidative stability as measured against a
l~f~,r~nce point of TERMAMYL~9 in comlll~,rc;al use in 1993. These plef~ d amylases
herein share the chalaL~.islic of being "stability~h~nred" amylases, chalacL~,.ized, at a
...;n;....-..., by a measurable improv.,~ll,nl in one or more of: oxidative stability, e.g., to
25 hydrogen peroxide/tetraac~l~lelh~ nfdi-...;n~ in buffered solution at pH 9-10; thermal
stability, e.g., at co.. on wash te~ .. ...ul~s such as 60~C; or ~ lin~ stability, e.g., at a
pH from 8 to 11, ~easul~d versus the above-identifi~d l~,f, rence-point amylase. Stability
can be ll,easul ~ using any of the art~icrlosed ~ech.~ l tests. See, for example, r~.f~ ~e.~ces
~licclosetl in WO 9402597. Stability l ..h~ ed amylases can be obtained from Novo or from
30 t~ .- nror International. One class of highly preferred amylases herein have the
collllllonality of being derived using site-directed mutagenesis from one or more of the
Rn~ amylases, especiqlly the R~ a-amylases, regardless of whether one, two or
multiple amylase strains are the ;.... ed;qte precursors. Oxidative stability-enhqnred
amylases vs. the above-i~l~ntifiPd ~fe~ence amylase are plefe,l.,d for use, especially in
35 bl~hi~g, more preferably oxygen ble2~hing, as distinct from chlorine blevqching,
.. ...
CA 02255005 1998-11-17
WO 97/43394 PCT/US97/08445
32
detelge.-t compositions herein. Such preferred arnylases include (a) an arnylase according to
the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a
mutant in which substitution is made, using alanine or threonine, preferably tll,~,onilK, of
the methionine residue located in position 197 of the B lich~i~iJ'or,,.is alpha-amylase, known
5 as TERMAMYL~, or the homologous position variation of a similar parent arnylase, such
as B. amyloliql ~iens, B. subtilis, or B. stearothermophilus; (b) stability enh~nced
amylases as desclibed by Cenellcor L~ alional in a paper entitled "Oxidatively R~sict~nt
alpha-Amylases" pr~s.~ Pd at the 207th A l.e.ican ChPmir~l Society National Meeting,
March 13-17 1994, by C. ~~ on. Therein it was noted that bleaches in ~J~o"~t
10 dishwashing de~ergel-ts inactivate alpha-amylases but that improved oxidative stability
amylases have been rnade by Ce~ ror from B. Iicl~ o",.~s NCIB8061. Melt.io~
(Met) was i~entifi~d as the most likely residue to be m~ified. Met was substi~ d one at
a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific m~ nts,
particularly iu~ t being M197L and M197T with the M197T variant being the most
15 stable eA~r~,ssed variant. Stability was nR8~ d in CASCADE~ and SUNLIGHT~9; (c)
particularly ~.ef.,~ed amylases herein include amylase variants having additional
mf-(lifir~tion in the ;..~ te parent as desc.ibed in WO 9510603 A and are available
from the ~c.ci~n~e~ Novo, as DURAMYL~g). Other particularly pl~f~-c;d oxidative stability
enh~--red amylase include those desc.ibed in WO 9418314 to C;e ~ .ror Int. .l18lional and
WO 9402597 to Novo. Any other oxidative stability e-~h~nce~l amylase can be used, for
example as derived by site-directed m~ en~si~ from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other plef. .-~ enzyme ~I~o~l;lic~ions are
accessible. See WO 9509909 A to Novo.
Other amylase enzymes include t_ose desc~il~d in WO 95/26397 and in co-~
application by Novo Nordisk PCT/DK96/00056. Specifi~ amylase e.l~.~llRS for use in the
dete~ co o;~;l;olls of the present invention include a-amylases ch8l8cle.i~d by having
a s~if.c activity at least 25 % _igher than the specific activity of Termamyl~ at a
te.n~alulc range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by
the Phadebas~9 a-amylase activity assay. (Such Ph~e~ a-amylase activity assay isdescribed at pages 9-10, WO 95/26397.) Also in~lu(le~ herein are a-amylases which are at
least 80~ homologous with the amino acid seq~len~es shown in the SEQ ID listings in the
~efe.~ ces. These enzymes are preferably h~cOll,olated into laundry det~,.g~
compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total
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33
composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the
total composition.
C'ell~ c~s usable herein include both bact~,.ial and fungal types, preferably having a pH
Optillllllll bel~,.een 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984,
discloses suitable fungal celll~l~ces from Humicola insolens or Humicola strain DSM1800
or a celh~l~ce 212-pro~h~ci~ fungus belonging to the genus Aeromonas, and cell~ ce
eAlla~lcd from the hepatc.p~as of a marine mollusk, Dolabella Auricula Solander.Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
10 2.247.832. CAREZYME~ and CELLUZYME~ (Novo) are especi~lly useful. See also
WO 9117243 to Novo.
Suitable lipase enzymes for det~r~,el~t usage include those produced by microorg~;cl~lc of
the Pseudomonas group, such as Pseudomonas stu~zen ATCC 19.154, as disclosed in GB
15 1,372,034. See also lipases in Jap~n~se Patent Application 53,20487, laid open Peb. 24,
1978. This lipase is available from Amano ph~ ie?l Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," or ~Amano-P." Other suitable co,lu,,.rcial
lipases include Amano-CES, lipases ex Chromoba~ter viscosum, e.g. Chromobacter
viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
20 Chromobacter vi~eosl<m lipases from U.S. Bioc~ r~l Corp., U.S.A. and Disoynth Co.,
The Nc~ ds, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived
from Humicola lanuginosa and collu~r~idlly available from Novo, see also EP 341,947,
is a l)ref~ d lipase for use herein. Lipase and amylase variants stabilized against
peroxidase enzymes are desclibed in WO 9414951 A to Novo. See also WO 9205249 and
25 RD 94359044.
In spite of the large l~ber of publications on lipase enzymes, only the lipase derived from
Humicola lanuginosa and produced in Aspergill~s oryzae as host has so far found
widesl,l. ad a~lication as additive for fabric washing products. It is available from Novo
30 Nordisk under the tra~ ç Lipolasen', as noted above. In order to o~ the stainremoval perfo~ ce of Lipolase, Novo Nordisk have made a llum~. of variants. As
des_lil~d in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase
i~llpl~o~.s the lard stain removal efficiency by a factor 4.4 over the wild-type lipase
(enzymes CO"",al. d in an amount r~gh~g from 0.075 to 2.5 mg protein per liter).35 Research Disclosure No. 35944 published on March 10, 1994, ~y Novo Nordisk discloses
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34
that the lipase variant (~:)96L) may be added in an amount coll~sl,o~lding to 0.001-100- mg
(5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides
the benefit of improved ~ll;t~ SS mq;..~ n-e on fabrics using low levels of D96L variant
in detelgent compositions contqining the bis-AQA surfq-rtq-ntc in the ~ icclosedherein, especially when the D96L is used at levels in the range of 50 LU to 8500 LU per
liter of wash solution.
C~ltinqce enzymes suitable for use herein are described in WO 8809367 A to ~e--r l~'Or.
Peroxidase enzymes may be used in combination with oxygen sources, e.g., p~lc~l,onate,
~,.I,ol.-te, hydrogen peroxide, etc., for "solution blP'~hi.~g" or prevention of ll~f~l of
dyes or pigm~ntc removed from substrates during the wash to other SUb~llat~S present in
the wash solution. Known peroxidases include hul~e.adish peroxidase, ligninqce, and
haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-co..~ g det.,l~.lt
compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.
A range of er~y-llc n~lials and means for their incorporation into ~ ic d~.t. l~lll
compositions is also disclosed in WO 9307263 A and WO 9307260 A to G. I~ ,~or
Int~"~lional, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty
et al. Enzymes are further ~ clQsed in U.S. 4,101,457, Place et al, July 18, 1978, and in
U.S. 4,507,219, ~ gh~s, March 26, 1985. Enzyme materials useful for liquid det~"E,e
forrn~lq-tions~ and their illcol~lalion into such formulations, are disclosed in U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in deterge.l~ can be stabilised by
various techni~l~es. Enzyme stabili~q~ion t~hniT-es . re disclosed and exemplified in U.S.
3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,
Venegas. Enzyme stabilisation ~ ~s are also described, for eA~I~ple, in U.S.
3,519,S70. A useful Rarillllc, sp. AC13 giving prot~ases, xylanases and cellulases, is
de~c~,bed in WO 9401532 A to Novo.
Enzyme Stabilizing System
The enzyme-cont-q-ining colll~sil ;(mc herein may optionally also comyl,se from 0.001 ~ to
10%, preferably from 0.005 % to 8 %, most preferably from 0.01 % to 6%, by weight of an
el~llR stabilizing system. The enzyme stabilizing system can be any stabilizing system
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which is compatible with the detersive enzyme. Such a system may be i~ ,e,llly provided
by other formulation actives, or be added set)alately, e.g., by the formulator or by a
mqmlfart lrer of detelgelll-ready enzymes. Such stabilizing systems can, for example,
comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic
S acids, and I~ ures thereof, and are design~d to address dirr. ,~ t stabilization problems
de~n~ling on the type and physical form of the dct~ ~ge,ll composition.
One stabilizing app.oach is the use of water-soluble sources of c~lril~m and/or l..ag.-f,si~
ions in the finich~ colll~osilions which provide such ions to the enzymes. ~lri~lm ions
10 are generally more effective than m~ ... ions and are plcÇ~ ,d herein if only one type
of cation is being used. Typical detergc~ll co~ osilions, especi~lly liquids, will co",l.lise
from about 1 to about 30, preferably from about 2 to about 20, more preferably from about
8 to about 12 millimoles of c~lril~m ion per liter of finichrd detc,g~ t collll)osiliol~, though
ValialiOIl iS possible ~ 1;ng on factors inrlu(ling the multiplicity, type and levels of
lS enzymes illCO~lat d. P~felably water-soluble c~lri~rn or m~.~f si~.. salts are employed,
inrl~ for example c~lrillm chloride, c~lri~m hydroxide, c~lrillm fol~Lt, c~lcil~m
malate, c~lci~m m~ te, c~lrillrn hy~vxide and c~lrillrn acetate; more generally, c~lri~lm
sulfate or ma~-rs;-l... salts coll~,spolldillg to the exemplified c~lrillrn salts may be used.
hCl h~leased levels of C~lri~m and/or l~g..~ci~ may of course be useful, for
20 example for promoting the grease-cutting action of certain types of surfactant.
Another stabilizing a~l,foach is by use of borate species. See Scve.soll, U.S. 4,537,706.
Borate stabilizers, when used, may be at levels of up to 10% or more of the co,ll~silion
though more typically, levels of up to about 3% by weight of boric acid or other borate
2S culll~uunds such as bora~ or oll~lobolaLe are suitable for liquid det~ use. .S~bsl;l.JI~
boric acids such as p~lylboro"lc acid, bu~neborol~ic acid, p-blonlophe.lylbolol~ic acid or
the like can be used in place of boric acid and reduced levels of total boron in d~l. .E,ent
co"lpos;l ;on~ may be possible though the use of such s~lb~ boron derivatives.
30 Stabilizing ~ ~"ls of certain cl~ni..g compositions, for example ~-tom~~ir dishwashing
compositions, may further comprise from 0 to 10%, preferably from 0.01% to 6% byweight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in
many water supplies from ~ rL i,~g and inactivating the enzymes, especially under ~Ik~lin~
condiliûns. While chlorine levels in water may be small, typically in the range from 0.5
35 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact
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36
with the el~y~l~c, for example during dish- or fabric-washing, can be relatively large;
accordingly, enzyme stability to chlorine in-use is som~timPs problematic. Sincepercarbonate has the ability to react with chlorine bleach the use of additional stabilizers
against chlorine. may, most generally, not be essentiql, though improved results may be
5 obtainable from their use. Suitable chlorine scavenger anions are widely known and
readily available, and, if used, can be salts contAinin~ .l,.oni lm cations with sulfite,
bisulfite, thioslllfite, thioslllf~t.~, iodide, etc. Antioxidants such as call,amate, ascorbate,
etc., organic amines such as ethyl~ iA...in.~ .acetic acid (EDTA) or alkiali metal salt
thereof, monoelllanolamine (MEA), and mixtures thereof can likewise be used. Likewise,
10 special enzyme inhibition ~y~L.,Ills can be incorporated such that different ~ .lLy-lles have
m~ximllm compatibility. Other conventional scave,lgels such as bisulfate, nitrate, cloride,
sources of hydrogen peroxide such as sodium pell~l_te tetrahydrate, sodium perborate
Illo,lohydrate and sodium pe,cOll,onate, as well as phosphate, co.~ e~l phosphate,
acetate, ber,7.5)~te, citrate, follllate, lactate, malate, tartrate, salicylate, etc., and Il~ ,S
15 thereof can be used if desired. In general, since the chlorine scavenger function can be
.r~"..lcd by ingredients sel,a._tely listed under better ..,cogniL~d rul~;liG~s, (e.g.,
hydrogen peroxide sources), there is no absolute reyuile,.l~ to add a separate chlorine
scaveng~l unless a cc,...~ performing that function to the desired extent is absent from
an el~rme conrAini~ embod;~ of the invention; even then, the scavenger is added only
20 for o~lim~lll, results. Moreover, the formulator will exercise a ch~ s normal skill in
avoiding the use of any enzyme scavenger or stabilizer which is majorly i~-ro,..l.Alible, as
form~ t~1, with other ~acli~e ingredients. In relation to the use of ammonium salts, such
salts can be simply ~lmiYed with the det~ .~e,lt composition but are prone to adsorb water
and/or liberate A--IIIIOI~ during storage. Accordingly, such materials, if present, are
desirably prot~,~t~d in a particle such as that described in US 4,652,392, P~agin~l~i et al.
Polymeric Soil Release AQent
Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be
30 employed in the present d~,tergenl cc,llposilions. If u~ili7~d, SRA's will generally coll,p~ise
from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by
weight, of the colllposiLion.
~efe"~,d SRA's typically have hydrophilic se~llRnt~ to hydrophilize the surface of
35 hydrophobic fibers such as polyester and nylon, and hydrophobic seg~ rl~ to deposit upon
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37
hydrophobic fibers and remain adhered thereto through completion of washing and rinsing
cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains
oc~ ing subseql~en~ to tl~-t- f n~ with SRA to be more easily cle~n~A in later washing
l,loce.l-lr~s.
SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S.4,956,447), as well as l-o~ a~ged mQno...fl units and structures may be linear, b~ clled
or even star-chaped. They may include capylllg ll.oieties which are especiqlly effective in
controlling molecular weight or altering the physical or surface-active pluy.,lies.
10 Slluclu~es and charge di~ lions may be tailored for application to dirf~.ent fiber or
textile types and for varied d.te.gelll or det.,.~e.ll additive ~,i~lu.,ls.
~f._~led SRA's include oligolll..ic tere~.h~ te esters, typically ple~ ed by processes
involving at least one ~ t,~,irlcalion/oligolll..i~lion, often with a metal catalyst such as
15 a ~ ..(IV) qlkoxide Such esters may be made using additional Illo~ol~ , ca~)âbl~ Of
being i~oll,olat~,d into the ester SLIuClulc through one, two, three, four or more positions,
wilhuul of course fol.lling a densely crosslinked overall sl.uclul .
Suitable SRA's include: a sulronated product of a sul.~ lly linear ester oligomer
20 co.~ ised of an oli~,om~lic ester backl.olle of t,lephlhqloyl and oxyaLkyleneoxy repeat
units and allyl-derived sulronat~,d ~ l moieties covalently q~ d to the backbone, for
e~ le as described in U.S. 4,968,451, No~ ~l 6, 1990 to J.J. Sch~ibPl and E.P.GocsPlin' such ester oligolllcl~ can be plel)~C;I by (a) ethoxylating allyl alcohol, (b)
lle?cti~ the product of (a) with dimethyl tel~lJh~ q~P ("DMT") and 1,2-propylene glycol
25 (nPGn) in a two-stage ~ crification/ oligol,Rli~tion ploce.lure and (c) le~cl~ng the
product of (b) with sodium metabisulfite in water; the non.ollic end-capped 1,2-propylene/pol~u~ lene tel~h~ l~te polyesters of U.S. 4,711,730, Dece-..kl 8, 1987
to G~osselirlk et al, for c~ple those produced by ~ c j~ ir~caliol~/oligoll~ ~lion of
poly(ethylel~l~/col) methyl ether, DMT, PG and poly(ethyleneglycol) (nPEGn); the partly-
30 and fully- anionic-end-capped oligo~ ,lic esters of U.S. 4,721,580, January 26, 1988 to
Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
hydroxyoct-q-nPs~llfonate; the nonionic-capped block polyester OligOnh~iC col.lpo~l"ds of
U.S. 4,702,857, October 27, 1987 to Gosselirlk~ for example produced from DMT, Me-
capped PEG and EG and/or PG, or a coll,bil~ation of DMT, EG and/or PG, Me-capped35 PEG and Na~i,lle~ l-S-sulfoisophthql3t~o; and the anionic, especially sulfoaroyl, end-
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38
capped te.elJh~ te esters of U.S. 4,877.896, October 31, 1989 to Maldonado, Gosselink
et al, the latter being typical of SRA's useful in both laundry and fabric conditioning
products. an example being an ester composition made from m-sulfobenzoic acid
monosodium salt, PG and DMT optionally but preferably further comprising added PEG,
e.g., PEG 3400.
SRA's also include simple copolymeric blocks of ethylene t~.ephlh~l~t~P or propylene
t,repht~ e with polyethylene oxide or polypropylene oxide le~,})hlh'~l~tP~ see U.S.
3,959,230 to Hays, May 25,1976 and U.S. 3,893,929 to R~c~ , July 8,1975; cell--losic
10 derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from
Dow; and the Cl-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093,
Decenlbe. 28,1976 to Nicol, et al. Suitable SRA's charac~ ised by poly(vinyl ester)
hydrophobe scE...- ~Ic include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl
esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See
Euro~all Patent Applir~ioll 0 219 048, published April 22, 1987 by Kud, et al.
Co,lull~ ;ially available examples include SOKALAN SRA's such as SOKALAN HP-22,
available from BASF, C~ .y. Other SRA's are polyesters with repeat units cont~ini~
10-15% by weight of ethylene ~ .lh~ tP together with 90 80% by weight of
polyoxyethylene le~c~ tP, derived from a polyoxyethylene glycol of average molecular
weight 300-5,000. Collul~ ;ial examples include ZELCON 5126 from Dupont and
MILEASE T from ICI.
Another plefe.l.,d SRA is an oligomer having e.llpirical formula
(CAP)2(EG/PG)s(T)s(SIP)1 which co~ .lises terephthaloyl (T), sulfoisophthaloyl (SIP),
25 oxyethyle.l~o~y and oxy-1,2-propylene (EG/PG) units and which is preferably t~_in~e~
with end caps (CAP), preferably m~ifi~d isethionates, as in an oligomer Colll~ illg one
sulfoico~h~ )yl unit, S t~,r~lllaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy
units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end~ap units
derived from sodium 2-(2-hyd~ yethoxy)~ll.znP~.~Ifonate. Said SRA preferably further
colll~iises from 0.5% to 20%, by weight of the oligomer, of a cryst~llinity-re~ ci.~g
stabiliser, for example an anionic ~ulr~ such as linear sodium dodecyl~.-7~.-fs~1fonate
or a ~lle,ll~l selPctP~ from xylene-, ~ f-, and toluene- sulfonates or mixtures thereof,
these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S.
5,415,807, Gosselin~, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for
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39
the above SRA include Na 2-(2-hydroxyethoxy)-eth~n~sl~lfonate, DMT, Na- dimethyl 5-
sulfoisophrh~l~te, EG and PG.
Yet another group of preferred SRA's are oligomeric esters colllplising: (1) a backbone
5 comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates,
polyhydroxy sulfonates, a unit which is at least trifunctional wllereby ester linkages are
formed resl~lting in a bl~nched oligomer bac~one, and combinations thereof; (b) at least
one unit which is a tel~hlhaloyl moiety; and (c) at least one unsulfonated unit which is a
1,2-oxyalkyleneoxy moiety; and (2) one or more capping units select~l from nonionic
10 capping units, anionic capping units such as alkoxylated, preferably ethoxylated,
isethionates, allcoxylated prop~n~s.llfol~t~,s, alkoxylated proy~--r~ lfonates, alkoxylated
phenolsulforlates, sulfoaroyl derivatives and ~ ules thereof. P~fel.~d of such es~ers are
those of c.llyilical formula:
{ (CAP)x(EG/PG)y ' (DEG)y n (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}
wll~le~ CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) l.,~l~s_~b
di(oxyethylene)oxy units; (SEG) ~ lc.se~ls units derived from the sulfoethyl ether of
glyce,in and related moiety units; (B) ~ep.es..lts bl~nl~hi~g units which are at least
,lir ~ whereby ester linl~ges are formed resultir~ in a b~ ched oligomer
20 bac~l.une; x is from about 1 to about 12; y' is from about 0.5 to about 25; y" is from 0 to
about 12; y" ' is from 0 to about 10; y' +y" +y" ' totals from about 0.5 to about 25; z is
from about 1.5 to about 25; z' is from 0 to about 12; z + z' totals from about 1.5 to about
25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y', y",
y"', z, z', q and m ~e~les~ the average ~ of moles of the corresponding units per
25 mole of said ester and said ester has a molecular weight raulging from about 500 to about
5,000.
~ef~ ed SEG and CAP ...~ for the above esters include Na-2-(2-,3-
dihydroxypropoxy)~ s ~lfonate ("SEGn), Na-2-{2-(2-hydroxyethoxy) ethoxy}
30 ~lh~n~ fonate ("SE3n) and its homologs and n~ixtures thereof and the products of
ethoxylating and sulfol~ling allyl alcohol. ~.~ lcd SRA esters in this class include the
product of ~IA...~ J . irying and oligolll~ lg sodium 2-{2-(2-
hydroxyethoxy)ethoxy}e~ n~..1fonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-
ethoxy}ethoxy]e~ nP,.~Ifonate, DMT, sodiurn 2-(2,3-dihydroxypropoxy) ethane sulfonate,
35 EG, and PG using an a~ oylialc Ti(IV) catalyst and can be ~lesipn~ted as
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(CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O3S[CH2CH2O]3.5)-
and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by
conventional gas chromatography after complete hydrolysis.
5 Additional classes of SRA's include (I) nonionic terephth~l~tes using diisocyanate coupling
agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S.
4,240,918 ~g~se et al; (II) SRA's with carboxylate tcllnil~al groups made by adding
trim~lliti~ anhydride to ~nown SRA's to convert te.ll.inal hydroxyl groups to trimellitate
esters. With a proper selection of catalyst, the trim~llitic anhydride forms linkages to the
10 tc.llf.llals of the polymer through an ester of the isolated carboxylic acid of trim~olliti~
anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic
SRA's may be used as starting materials as long as they have hydroxyl terminal groups
which may be e;.l~ified. See U.S. 4,525,524 Tung et al.; (m) anionic te~ te-based
SRA's of the u~~ c-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl
15 caprolactam) and related co-polymers with nlollunRl~ such as vinyl pyrrolidone and/or
,lhyl~minoethyl ..~ ~ylate, inrl~ in~ both l~O~iOlllC and calion,c polymers, see U.S.
4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from
BASF made, by g~afling acrylic lllUnUIII~ on tO sulfol~t~d polyesters; these SRA's
assertedly have soil release and anti-redeposition activity sirnilar to known ce~ ose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl ~llono-l.~.s such as
acrylic acid and vinyl acetate on to pro~cills such as caseins, see EP 457,205 A to BASF
(1991); (VII) polyester-polyamide SRA's pll,pal~d by con~len~ing adipic acid, caprolactam,
and polyethylene glycol, especially for llca~ g polyamide fabrics, see Bevan et al, DE
2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents
4,240,918, 4,787,989, 4,525,524 and 4,877,896.
Cla~,r Soil Removal/Anti-led.,~;,ilion A~ents
The coll.l,osiliol~s of the present invention can also optionally contain water-soluble
30 ethoxylated amines having clay soil removal and antiredeposition pro~. Lies. Granular
~telge.lL compositions which contain these compounds typically contain from 0.01 % to
10.0% by weight of the water-soluble ethoxylates amines; li~uid d~,tel~ent compositions
typicallycontainO.01% to5%.
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41
The most pref~ ,d soil release and anti-redeposition agent is ethoxylated tetraethylene-
pem~min~. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898,
VanderMeer, issued July 1, 1986. Another group of plefell~d clay soil removal-
aIlli.edeposition agents are the cationic coll.puunds disclosed in European Patent
Application 111,965, Oh and Gosselin'c, published June 27, 1984. Other clay soilremoval/antiredeposition agents which can be used include the ethoxylated amine polymers
disclosed in European Patent Application 111,984, Gosselinlc, published June 27, 1984; the
~vilL.,.ionic polymers ~icclosecl in Euro~an PateM Application 112,592, Go.sselirlc,
published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor,
10 issued October 22, 1985. Other clay soil removal and/or anti redeposition agents Icnown in
the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160,
Vande.Meer, issued January 2, 1990 and WO 95/32272, published Nov~l"~, 30, 1995.Another type of pref~ d antiredeposition agent ~n~ludes the carboxy methyl cellulose
(CMC) materials. These materials are well known in the art.
Polymeric Dl~ A~ents
Polymeric disL~ g agents can advantageously be utilized at levels from 0.1 % to 7 %, by
weight, in the colll~o~ilion~ herein, especially in the p.es~.~ce of zeolite and/or layered
20 silicate builders. Suitable polymeric di~ lg agents include polymeric polycarboxylates
and polyethylene glycols, ~lthol)gh others known in the art can also be used. It is believed,
though it is not intPn~ to be limited by theory, that polymeric disl,c.sillg agents enh~n~e
overall del.,.ge.ll builder pe.~u~lllance, when used in co...bi~ation with other builders
(in~ .ting lower molecular weight polycarboxylates) by crystal growth inhibition,
25 particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be plet)~cd by polyl..e.~ing or copolyllR~ g
suitable uns,.lu-at._d ...O~ , prLf~,,ably in their acid form. Unsaturated muno.l.elic
acids that can be poly.--c.ized to form suitable polymeric polycarboxylates include acrylic
30 acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,
mesaconic acid, citraconic acid and methylerl~m~lonic acid. The l,.esence in the polymeric
polycarboxylates herein or monom~ric seE,..~ , con~ining no carboxylate radicals such as
vill~ lctllyl ether, styrene, ethylene, etc. is suitable provided that such s~ ,nls do not
constitute more than 40% by weight.
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Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such
acrylic acid-based polymers which are useful herein are the water-soluble salts of
polymerized acrylic acid. The average molecular weight of such polymers in the acid form
preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most
preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can
include, for example, the alkali metal, ammonium and substituted aln~lloniL~Ill salts.
Soluble polymers of this type are known materials. Use of polyacrylates of this type in
dete.gelll compositions has been ~ close~ for example, in Diehl, U.S. Patent 3,308,067,
issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a plefe.l..d colll~l~ t of the
dis~,~ing/anti-redeposition agent. Such materials include the water-soluble salts of
copolymers of acrylic acid and maleic acid. The average molecular weight of suchco~olyll.~l~ in the acid form pl.,fe.abl~ ranges from 2,000 to 100,000, more preferably
from 5,000 to 75,000, most pl~f.,lably from 7,000 to 65,000. The ratio of acrylate to
mqlP~te se~lll.,n~ in such copolymers will generally range from 30: 1 to 1: 1, more
preferably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid
copolymers can include, for t~llple, the aL~cali metal, ammonium and S~lbS~ t~d
~Illlloniulll salts. Soluble acrylate/m~lPqte copolymers of this type are known materials
which are desclibcd in Eulu~an Patent Application No. 66915, published Dec~mher 15,
1982, as well as in EP 193,360, published Sel)telllber 3, 1986, which also des. libes such
polymers colllplisillg hydro~Ly~ropylacrylate. Still other useful dis~lsii~g agents include
the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, inr!u(~ing, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another pol~u~.,lic material which can be in~ludPd is polyethylene glycol (PEG). PEG can
exhibit di;.~ ing agent pelf.~ e as well as act as a clay soil removal-all~ir~eposition
agent. Typical molecular weight ranges for these purposes range from 500 to 100,000,
preferably from 1,000 to 50,000, more plefelably from 1,500 to 10,000.
Polyaspal~e and polygl..~ dis~ g agents may also be used, especially in
conjun~lion with zeolite builders. Dis~sing agents such as polyaspartate preferably have
a molecular weight (avg.) of 10,000.
B~ r
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43
Any optical bri~l.t~ ~-1... or other brighte~ ing or whitening agents known in the art can be
incorporated at levels typically from 0.01 % to 1.2%, by weight, into the dete;g~
compositions herein. Co~ .c,cial optical brig~lrl~ 1'7 which may be useful in the present
5 invention can be clq-ccified into subgroups~ which include, but are not ~ Cf ss~rily lhnited
to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, ...r!l.;nfcyanines,
u~lliophf nf -5~5-dioxide~ azoles, 5- and 6-..u ~~'~rf d-ring h~t~,lo~;ycles, and other
miccellqnf ous agents. Examples of such bri~ -f ~. are disclosed in "The Production and
Application of FluorescellL ~ t~ g Agents", M. Zahradnik, Published by Jonn Wiley
10 & Sons, New York (1982).
Specifil ~Aa ll~les of optical bri~l.t-r n., ~. which are useful in the present c~ posilions are
those iderltifi~ in U.S. Patent 4,790,856, issued to Wixon on Decf. ..l;~r 13, 1988. These
bri~l~t~ include the PHORWHITE series of brigl~ from Verona. Other
lS bright'F'- lS rlicclosed in this l~f~.ellce include: Tinopal UNPA, Tinopal CBS and Tinopal
SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-
phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbPnPs; 4,4'-
bis(styryl)bi~h~,lyls; and the ~ oco~-..q. ins. Specific exarnples of these bri~ f ~f ~s
include 4-methyl-7-diethyl- amino colullalin; 1,2-bis(~n~;,..iA~7Ol-2-ylkthylene; 1,3-
diphenyl-pyrazolines; 2,5-bis(ben7oxq-7Ql-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole;
and 2-(stilben4-yl)-2H-n~rhtho[1,2-d]triazole. See also U.S. Patent 3,646,015, issued
February 29, 1972 to E~miltc-n
Dye Transfer Inhibitinp Agents
The COI~ ;0~ of the present invention may also include one or more rnaterials effective
for inhi~ g the ll~f~,r of dyes from one fabric to another during the cleqning process.
Generally, such dye ~ , ulhi~ g agents include polyvinyl pyrrolidone polymers,
polyamine N~xide polyrners, copolymers of N-vinylpyrrolidone and N-vinylimi~J~7ole,
30 ~gi~nrse phthalocyanine, peroxidases, and mixtures thereof. If used, these agents
typically comprise from 0.01 % to 10% by weight of the composition, preferably from
0.01% to 5%, and more preferably from 0.05% to 2%.
More specifically, the poly~ul.il1e N-oxide polymers preferred for use herein contain units
having the following structural formula: R-AX-P; wherein P is a polymerizable unit to
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44
which an N-0 group can be ~ rh~d or the N-0 group can form part of the polymerizable
unit or the N-0 group can be ~ ~h~-~ to both units; A is one of the following structures -
NC(0)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics,
aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen
S of the N-0 group can be alt~rh~l or the N-0 group is part of these groups P~f~ d
polyamine N-oxides are those wherein R is a h~,t, lu ~clic group such as pyridine, pyrrole,
imi~l~701e, pyrrolidine, piperidine and derivatives thereof
The N-0 group can be .~p~se,lt~d by the following general sL~u~;lulcs:
1~
(Rl)x 7 (R2)y; =N (Rl)x
(R3)z
wllc. hl Rl, R2, R3 are ~lirh"~i~, al~ulatic, h~ro~;yclic or alicyclic groups orco..lbil~lions thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be
15 ~tt ~h~d or form part of any of the afo.~ nlioned groups The amine oxide unit of the
polyamine N-oxides has a pKa c 10, preferably pKa <7, more p..,fe..ed pKa c6
Any polymer backbone can be used as long as the amine oxide polymer formed is water-
soluble and has dye ~f._, inhibi~ g pio~.lies. Examples of suitable polymeric
20 backbones are polyvinyls, polyaL~ylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and llli~ lCS thereof. These polymers include random or block copolymers
where one mono~ r type is an amine N-oxide and the other l~lollu~ type is an N-oxide
The amine N-oxide poly~ s typically have a ratio of amine to the amine N-oxide of 10:1
to 1 1,000,000. However, the u~ ber of arnine oxide groups present in the pol~d.~.e
25 oxide polymer can be varied by ap~ropl.atc copolyl~ ion or by an applu~liate degree
of N-oxidation The pol~e oxides can be obtained in almost any degree of
pol~ll.e~alion. Typically, the average molecular weight is within the range of 500 to
1,000,000; more prcf~ d 1,000 to 500,000; most plefe,led 5,000 to 100,000 This
p.cfe,.~d class of materials can be r~,fe,led to as "PVNOn
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The most l).cfell~d polyamine N-oxide useful in the del_lgent compositions herein is
poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an
amine to amine N-oxide ratio of 1:4.
5 Copolymers of N-vinylpyrrolidone and N-vinyl;...i-1~70le polymers (referred to as a class as
"PVPVI") are also plef._..ed for use herein. Preferably the PVPVI has an averagemolecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
.,..in~l by light scalte~u~g as described in Barth, et al., Ch~mi~l AnalYsis. Vol 113.
10 "Modern Methods of Polymer Chara~;le.~lionn, the disclosures of which are incorporated
herein by r~fcrf,lce.) The PVPVI copolymers typically have a molar ratio of N-
vinylimi~1~7ole to N-vi~l~ olidone from 1:1 to 0.2:1, more p.cf~,,dbly from 0.8:1 to
0.3: 1, most preferably from 0.6: 1 to 0.4:1. These copolymers can be either linear or
b,~lched.
The present invention co...~ilions also may employ a polyvinylpyrrolidone ("PVPn)
having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to
200,000, and more pl~Çf~ably from 5,000 to 50,000. PVP's are known to persons skilled
in the d~t~ige.ll field; see, for example, EP-A-262,897 and EP-A-256,696, iulco~at~d
20 herein by ~f~_re.~ce. Co.-.posiliolls cont~inin~ PVP can also contain polyethylene glycol
(nPEG") having an average molecular weight from 500 to 100,000, preferably from 1,000
to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions
is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
The d t,~g~ con~rositi~ns herein may also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical bri&l.t~ rs which also provide a dye L.ar~r.,r
inhibition action. If used, the co.~lpo~i~;o~c herein will preferably collll).ise from 0.01% to
1 % by weight of such optical ~ t~ r~.,~,.
The hydrophilic optical brigh~ nf,~ useful in the present invention are those having the
structural formula:
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46
RI~N H H N ~ 2
~\ /~\ I I / ~\ /~
N~)~N~C=C~ ~ I ~, /N
R2 SO3M SO3M Rl
wherein Rl is selectPd from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is
select~d from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro
5 and amino; and M is a salt-folllling cation such as sodium or pot~csil~m
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation
such as so~ m, the bri~htPrPr is 4,4',-bis[(4-anilino~-(N-2-bis-hydroxyethyl)-s-~ ine-2-
yl)amino]-2~2~-stilb-pnp~ic~llfonic acid and tlico~ m salt. This particular brightener species
10 is COI~ rcially Illa~ted under the trade~ c Tinopal-UNPA-GX by Ciba-Geigy
Col~oldlioll. Tinopal-UNPA-GX is the pltr~ d hydrophilic optical bri~htPnPr useful in
the dete.~ colllpo~;l;onc herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M
is a cation such as so ~ m, the bri~ .f ~ is 4,4'-bisl(4-anilino-6-(N-2-hydroxyethyl-N-
methylamino)-s-~ -2-yl)amino]2,2'-stilbel-f~ fonic acid disodium salt. This
particular ~ htenfr species is collllllel~ially ll~t~d under the tr~d~Pn~mP Tinopal SBM-
GX by Ciba-Geigy Col~l on.
20 When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as
so~ m, the bri~l~t~ is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-
stilhe~ fonic acid, sodium salt. This particular bri~ f l species is col~ ciallyrl.. ~d uDder the tradename Tinopal AMS-GX by Ciba Geigy Col~olalion.
25 The specific optical bri~ht~npr species selected for use in the present invention provide
especi~lly effective dye ~l~r~. inhibition performance bel~rl~ when used in colllbil~tion
with the selectP~l polymeric dye ,l~r~r inhibiting agents hcleillbcfore dcsclibed. The
colllbi~ ion of such sel~ polymeric materials (e.g., PVNO and/or PVPVI) with such
sele~ d optical bri~l.t~ ~rls (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal
3Q AMS-GX) provides signifir~ntly better dye transfer inhibition in aqueous wash solutions
than does either of these two dete~gent composition colllpoll..lts when used alone. Without
. ~
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47
being bound by theory1 it is believed that such brigl.lPrl ., work this way because they have
high affinity for fabrics in the wash solution and therefore deposit relatively quick on these
fabrics. The extent to which brighlene.~, deposit on fabrics in the wash solution can be
defined by a pararneter called the "exh~ lstion coefficient". The exhqlJstion coefficient is in
5 general as the ratio of a) the br;gl~ material deposited on fabric to b) the initial
brigl.l~ nf ~ conc..~ tion in the wash liquor. Bri~ f .~ with relatively high e xh-qn~tion
coefficients are the most suitable for inhibiting dye ~ ,r~. in the context of the present
invention.
10 Of course, it will be appl~ciated that other, conventional optical brightf nPr types of
co...pou,lds can optionally be used in the present cclllposilions to provide conv.ul;Qnql
fabric '~briehtnf ss~ benef~" rather than a true dye ~ r~. inhibiting effect. Such usage is
conventional and well-known to dcl~ lg~nt formulations.
15 Chf 1~ Ag~nt~
The df te~gf ~1l compositions herein may also optionally contain one or more iron and/or
nf'Sf. rh~l~li"~ agents. Such chelating agents can be selec~ed from the group
cnnC;~ of amino car'ooxylates, amino phospho~ s~ polyfunctionally-s~lbsl;n.~d aro-
20 matic chFl~ agents and mixtures therein, all as hereinafter defined. Without intf n~lin~to be bound by theory, it is believed t'nat the benefit of these rnaterials is due in part to
their exce~lional ability to remove iron and l..~eAn~se ions from WdShing solutions by
forrnqtion of soluble chfl~t. r7
25 Amino carboxylates useful as optional ch~lAI ;-~g agents include ethylen-P~ . aretA~ s,
N~ lro~lethylen-P~ ..;n. h;~et-q-t~s, nitrilo~ fs, ethyl~ ~fliA~...n~
t~ a~iO~IiOnateS~ triethYIen~te~ hr}~ et-q-t~OS~ diethYIe~ ;n~PenlA-qret~qtPS, and
eth~ lycines, aL~cali metal, ~.. nn;.~.. " and ~ub~lilut~d qmmonillm salts therein . nd
lUlCS therein.
Amino phosphonqtes are also suitable for use as ch-Pl-q-ting agents in the compositions of the
invention when at least low levels of total phosphorus are ~I.liued in d~t~ ,enlcolllposilions, and include ethylen-P~iq-min-Pt~Ptrakis (methylenephosphol~hs) as DEQUEST.
~ fe,l~d, these amino phosphonates to not contain alkyl or aLkenyl groups with more than
35 6 carbon atoms.
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Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et ah P~f.,.l~,d
compounds of this type in acid form are dihydroxydisulfobenzel~es such as 1,2-dihydroxy-
5 3,5-disulfobel~Le.l~.
A y~efe.l. d biodegradable chelator for use herein is ethylen~ min~ disuccinate
("EDDSn), especiqlly the [S,S] isomer as dcsclibed in U.S. Patent 4,704,233, Nove~
3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine .1i~retir acid
(MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble
builders such as zeolites, layered .cilir~e~.
If Utili7~1, these chr!~ agents will generally co,--y.ise from 0.1 % to 15 % by weight of
the dcte~ge.ll con.yosilions herein. More p~efelably, if lltili7Pf1, the chP~ agents will
co.l.y.ise from 0.1 % to 3.0% by weight of such comyosilions.
Suds Suy~)~ssors
Conlyo~ ds for reducing or ~uyyu~,~sillg the formation of suds can be incolyolal~d into the
colll~osilions of the present invention. Suds ~iUyp~eSsioll can be of particular irnportance in
the so-called "high COllC~.~t~aliOl1 cle~ni~ process" as described in U.S. 4,489,455 and
4,489,574 and in front-loading Eul~l~ean-style washing m~rllin.os.
A wide variety of materials may be used as suds sLIl~plessors, and suds ~uyyleSSOrS are well
known to those skilled in the art. See, for ex~--yle~ Kirk Otluner Encyclopedia of
Ch~mi~l Te~hn~ gy~ Third Edition, Volume 7, pages 430~47 (John Wiley & Sons, Inc.,
1979). One catL~o.~ of suds ~uy~lesso~ of particular interest encol~p~cses Illolloc~l,oxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960
to Wayne St. John. The ...onoc~.boxylic fatty acids and salts thereof used as suds
~uyylessor typically have hy-lroc&-l~yl chains of 10 to 24 carbon atoms, preferably 12 to 18
carbon atoms. Suitable salts include the aLkali metal salts such as so ~ m, pot~csillm~ and
lithium salts, and an,..lon,ull, and a1~canola,l,moluum salts.
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The det~ e.ll compositions herein may also contain non-surfactant suds suppressors.
These include, for example: high molecular weight hydrocarbons such as paraffin, fatty
acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic
Clg-C40 ketones (e.g., ~l~alone), eu. Other suds inhi~ilors include N-alkylated amino
S lli~il.es such as tri- to hexa-alkylm~l~min~s or di- to tetra-alkyl~ min~ chlortriazines
formed as products of cyanuric chloride with two or three moles of a primary or sccondalr
amine cont~ini~ 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such
as monost~ryl alcohol phos~h~te ester and monostearyl di-alkali metal (e.g., K, Na, and
Li) phosphates and phosphate esters. The hydl~carl,ons such as pa,arrl" and halolJararful
10 can be utilized in liquid form. The liquid hydroc~l,ons will be liquid at room tc~llpelatllle
and atmosph.,lic p~ u~, and will have a pour point in the range of 40~C and 50~C, and
a l..in;....~ boiling point not less thanllO~C (atmo~l,}~lic ~ s~e). It is also known to
utilize waxy hydrocarbons, preferably having a ...~ ..g point below 100~C. The
hy-llvc~l,u"s constitute a plefel,~d Cà~gOlr of suds supp.~sûr for dct~lg~ t
15 col,.posiliolls. Hydrocalllol1 suds su~ ssors are dcs.,libed, for example, in U.S. Patent
4,265,779, issuedMay5, 1981 toGandolfoetal. Theh~ocall,ons, thus, include
~lirh~tir, alicyclic, aromatic, and het~,.~yclic satula~d or unsaturated h~ldlocd,l,olls
having from 12 to 70 carbon atoms. .The term "pdlaîrlll," as used in this suds ~upl)ressûr
~ic~-..csion, is intPn~ed to include nIL~lUIeS of true paraffins and cyclic hydrocdrl,ulls.
Another plcf~.lcd cdtegolr of non-surfactant suds ~ulJplessors comprises silicone suds
~U~pl~SSvl~. This category inrllld~s the use of polyor~allosiloxane oils, such as
polydill~ hylsiloxane, dis~.~ions or em~lcions of polyorganosiloxane oils or resins, and
co."b~ations of polyo,g~-o~iloxqn~ with silica particles wll~.eil1 the polyorganosiloxane is
25 c~ o,l~ or fused ûnto the silica. Silicone suds ~u~p~ssors are well known in the art
and are, for e~u~>le, ~;~1QS~1 in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo
et al and ~o~ Patent Application No. 89307851.9, published Pebruary 7, 1990, by
Starch, M. S.
30 Other silicone suds ~u~pressol~ are disclosed in U.S. Patent 3,455,839 which relates to
compositions and processes for defoaming aqueous solutions by inco.~.~lating therein small
of polydil~ lsiloxane fluids.
Mixtures of silicone and sil~qnqt~d silica are desclil~d, for incl~ e, in German Patent
Application DOS 2,124,526. Silicone defoa.nel~ and suds controlling agens in granular
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detelge-~t compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S.
Patent 4,652,392, R~gin~ki et al, issued March 24, 1987.
An exemplary silicone based suds ~u~yl.,ssor for use herein is a suds SU~pl~SSillg amount
of a suds controlling agent col-c;~ sse~ 1y of:
(i) polydu-,.,lhylsiloxane fluid having a viscosity of from about 20 cs. to about
1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin
co.l,~osed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3
SiO1/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica
gel.
In the ~lefe.l~,d silicone suds ~upplessor used herein, the solvent for a contimlo~-~
phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol
15 copolymers or ~ ules thereof (~l~f~ ,d), or polyl,~o~lene glycol. The primary silicone
suds ~upplessor is b~ hed/crosslinl~d and preferably not linear.
To illustrate this point further, typical liquid laundry d~.t~.ge.ll co.llposilions with
controlled suds will optionally co~JI,lise from about 0.001 to about 1, preferably from
20 about 0.01 to about 0.7, most pl~fe.~bly from about 0.05 to about 0.5, weight % of said
silicone suds sllyplessor~ which comprises (1) a nonaqueous emulsion of a primary
~lliroa.ll agent which is a ~ , of (a) a polyolg~nosiloxane, ~b) a resinous siloxane or a
siliccn~ resin-pro~uci~ silicone colll~ul.d, (c) a finely divided filler material, and (d) a
catalyst to proll-~le the reac~iol~ of Ini~UI~ components (a), ~b) and (c), to forrn silanolates;
25 (2) at least one ~ ;o~iC~ siliron~ ~.ur~c,~ll; and (3) polyethylene glycol or a copolymer of
polyethylene-poly~lop,lene glycol having a solubility in water at room te~llpel~lule of
more than about 2 weight %; and without polypropylene glycol. Similar amounts can be
used in granular co~osi~io~, gels, etc. See also U.S. Patents 4,978,471, Starch, issued
Dec~ 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et
30 al., issued I~eblu~ 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at
column 1, line 46 through column 4, line 35.
The silicone suds ~u~ lessor herein preferably co..ll,lises polyethylene glycol and a
copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular
weight of less than about 1,000, preferably between about 100 and 800. The polyethylene
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glycol and polyethylene/polypropylene copolymers herein have a solubility in water at
room temperature of more than about 2 weight %, preferably more than about 5 weight %.
The preferred solvent herein is polyethylene glycol having an average molecular weight of
less than about 1,000, more preferably between about 100 and 800, most preferably
,ell 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol,
preferably PPG 200/PEG 300. Pr~fe,l~,d is a weight ratio of ~I~ n about 1:1 and 1:10,
most preferably ~t~ .n 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-
polypropylene glycol.
The preferred silicone suds SulJ~iessolS used herein do not contain polypropylene glycol,
particularly of 4,000 molecular weight. They also preferably do not contain block
copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
15 Other suds auppl~ SSOl~ useful herein conlplise the secondary alcohols (e.g., 2-alkyl
aL~canols) and ll~h~lures of such alcohols with silicone oils, such as the silicones disclosed in
U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16
aLkyl alcohols having a Cl-C16 chain. A ~r~fe.l~,d alcohol is 2-butyl octanol, which is
available from Condea under the llade~ ISOFOL 12. Mixtures of secondary alcohols20 are available under the trademark ISALCHEM 123 from F.nif ll~rn. Mixed suds
s,~ .ssors typically collll,lise nli~ules of alcohol + silicone at a weight ratio of 1:5 to
5:1.
For any d,_ler~,elll conlrositionc to be used in automatic laundry or dishwashing m~hin~s,
25 suds should not form to the extent that they either overflow the wdShillg ~ C~ or
negatively affect the washing ...~ ... of the dishwasher. Suds suppressors, whenili7Pd, are preferably present in a "suds :~up~-essing ~mollnt. By "suds supl)~ssing
~mmlnt" is meant that the formulator of the composition can select an amount of this suds
controlling agent that will s~ffi~iently control the suds to result in a low-sudsing laundry or
30 dishwashing detelgel.ls for use in " ~lo~ r laundry or dishwashing m~ in~s.
The colllposi~ions herein will generally comprise from 0% to 10% of suds ~u~ essor.
When utili_ed as suds ~u~L"essol~, monocarboxylic fatty acids, and salts therein, will be
present typically in amounts up to 5 %, by weight, of the d~lergen~ composition.35 Preferably, from 0.5% to 3% of fatty monocarboxylate suds sul l"essor is utili_ed.
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Silicone suds au~ressors are typically utilized in amounts up to 2.0%, by weight, of the
deterge.,l composition. although higher amounts may be used. This upper limit is practical
in nature, due primarily to conc~ll, with k.,epin~ costs minimi7eC~ and effectiveness of
lower ~mountC for effectively controlling sudsing. Preferably from 0.01 % to 1 % of
silicone suds ~up~ssor is used, more preferably from 0.2S% to O.S%. As used herein,
these weight ~,~;c.,Lage values include any silica that may be urili7~-l in co",bination with
polyolganosiloxane, as well as any optional materials that may be utilized. Monostearyl
phosph~te suds Sup~l~SSO15 are generally utilized in amounts lan~ing from 0.1 % to 2%, by
weight, of the composition. Hydl~ocallJon suds ~upp,~ssors are typically utilized in
10 ~ o~ r~l~h~g from 0.01 % to 5.0%, ~Ithol)gh higher levels can be used. The alcohol
suds ~upplessors are typically used at 0.2%-3% by weight of the finich~d compositions.
AlkoxYlated PolycarboxYlates
15 ALlcoxylated pol~;a~l,o~ylates such as those ~ ,d from polyacrylates are useful herein
to provide additional grease removal p~Ç~.I.llal~ce. Such materials are desclibed in WO
91108281 and PCT 90/0181S at p. 4 et seq., incorporated herein by refel~.lce.
Ch~o~nir~lly, these materials colllplise polyacrylates having one ethoxy side-chain per every
7-8 acrylate units. The side-chains are of the formula -(CH2CH20)m(CH2)nCH3 wlie.~,in
20 m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "bacl~bone" to
provide a "comb" polymer type structure. The molecular weight can vary, but is typically
in the range of 2000 to 50,000. Such alkoxylated polycar~oxylates can colllylise from
0.05% to 10%, by weight, of the compositions herein.
25 Fabric Sor~n~.~
Various through-tlle-. ~sh fabric sor~e.~, ecpeci~lly the imr~lp~hle S...~C~ clays of U.S.
Patent 4,062,647, Storm and Nirschl, issued Dec~-..her 13, 1977, as well as other softener
clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by
30 weight in the present co~ o~il;onc to provide fabric softener ~n~fi~ co~i~;ull.,.llly with
fabric cl~w.g. Clay sur~el~ can be used in co.llbil~tion with an~ine and cationic
softeners as Aisclose~1. for t;A~Ilyle, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983
and U.S. Patent 4,291,071, Harris et al, issued Se~t~.l.ber 22, 1981
35 ~. rwlles
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Perfumes and perfumery ingredients useful in the present compositions and processes
comprise a wide variety of natural and synthetic ch~mi~q-l ingredients, in~ludin~, but not
limited to, aldehydes, ketones, esters Also in~ ded are various natural extracts and
5 ess~ r~s which can con~lise complex ~ ul'~S of ingredients, such as orange oil, lemon
oil, rose extract, lavender, musk, p~. hollli, bal~qmi~ essc .~e, sandalwood oil, pine oil,
cedar Finished pe.rw-Rs can comprise ~l.c.llcly complex mixtures of such ingredients
Finished pc.rull.cs typically COIIl~lisc from 0 01% to 2%, by weight, of the dete~el.l
composiliulls herein, and individual p~ru~ y ingredients can co..lplise from 0 0001% to
10 90% of a r. .iChrd pelrunlc co.llposilion.
Non-limitin~ ples of pe.rulllc ingl~di~ s useful herein include: 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7 tel.~ne~.yl ~-aph~ PnP; ionone methyl; ionone gamma
methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-l-i.1,~ 1-2,5,9-
cyclo~lod~P~q~rien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hP~ hyl tetralin; 4-acetyl-6-tert-
butyl-l,l~imethyl indane; para-hydroxy-phenyl-b~ .-on~ zoph~nolx; methyl beta-
naphthyl ketone; 6-acetyl-1,1,2,3,3,5-h ~ 1 indane; 5-acetyl-3-iso~.opyl-1,1,2,6-
te~ l-yl indane; l-do~Pcqnql~ ~(4-hydroxy4-u~ll.yl~ yl)-3-cyclohexene-1-
carboxaldehyde; 7-hydroxy-3,7~i n~ yl ocqt~n-q-l; 10-~ ce~--l-al; iso-hexenyl cyclohexyl
carboxaldehyde; formyl tricyclodecqnP; con~len~qtiQn products of hydroxycitronellal and
methyl al,lh,allllate, co~ F ~ on pi~lu.;~ of hydroxycitronellal and indol, con~encqtion
products of phenyl ~cet-q~ hyde and indol; 2-methyl-3-(para-tert-butylph~.-~l)-
propionaldehyde; ethyl vanillin; heliotropin; hexyl C-~-n~n-il~ aldehyde; amyl ci~-n~ ~ ir
aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; COUIl~lill; ~lec-q-l""tone
g,qmm~; cyclopent-dec~n~ P; 16-L~d~o~y-9-hPY d~e~-oic acid lactone; 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-kf~ lcyclopenta-~amm~ 2-h.,~opyrane; h-eta-naphthol methyl
ether; ambroxane; ~Pc~hydro-3a,6,6,9a t~ t~a.nell.ylnaphtho[2,1b]furan; cedrol, S-(2,2,3-
Llh~l.,LI-ylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-t.hll~tllyl-3-cyclopel.le.l-1-
yl)-2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl
acetate; henzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.
Particularly ~ref.,~, d ~,ru l.e materials are those that provide the largest odor
improve,l,~ s in fini~hPd pr~lucL colllposilions cont~inin~ cellulases These ~Çullles
include but are not limited to: hexyl cinn~mic aldehyde; 2-methyl-3-(para-tert-
butylphenyl)-propionaldehyde; 7-acetyl-1,2 ,3 ,4,5 ,6,7 ,8-octahydro-1, 1 ,6,7-tl ~l~ne~.yl
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n~phth~1ene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl
cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-
naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-
hexahydro-4,6,6,7,8.8-h~s~m~thyl-cyclopenta-g~mm~ 2-bellzopyrane; do~ec~hydro-
5 3a,6,6,9a-tellalllel]lylt~ hlllo[2~lb]fura~ nic~l~ellyde; COIllllalin; cedrol; vanillin;
cyclopent~ ec~n~lide; tricycloA~cenyl acetate; and tricyclodecenyl propionate.
Other pe.ru---c ~..ate.ials include ~ccenti~t oils, resinoids, and resins from a variety of
sources inrlu-ling, but not limited to: Peru bqlc~m~ Olih~m~m r~si~loid, styrax, l~1~1~l..l...
10 resin, nutmeg, cassia oil, benzoil- resin, coriander and lavandin. Still other ~.rull.e
ch~mir~1c include phenyl ethyl alcohol, l~ eol, linalool, linalyl acetate, geraniol, nerol,
2-(l,l-dimethylethyl)-cyc1Oh~ nol acetate, benzyl acetate, and eugenol. Carriers such as
diethylrhthql~te can be used in the r..~;~h~d pe.r~,ll.e co~ o~ ;o~-c.
15 Other Ingl~,di.,ll~
A wide variety of other i-~l~;di.n~ useful in det~,.ge.ll co..ll os;~ions can be inrl~ eA. in the
co~,.posi~ions herein, inrh1Ain~ other active in~l~,die.~, carriers, hydlo~lopcs, processing
aids, dyes or E);gl~ t~, solvents for liquid forrnlll~tions, solid fillers for bar compositions,
20 etc. If high sl~Aci~ is desired, suds boosters such as the Clo-C16 aL~canol~miAes can be
h1col~ ated into the co...pos;liol-c, typically at l %-10% levels. The C lo-Cl4
and ~ nol amides illustrate a typical class of such suds boosters. Use of
such suds boosters with high s~cing optional s~ r~ such as the amine oxides,
betaines and s~1t~ir Pc noted above is also advantageous. If desired, water-soluble
I.. agnf S;ll~.~ andJor c~lri1~rn salts such as MgC12, MgSO4, CaC12 CaS04, can be added at
levels of, typically, 0.1%-2%, to provide additional suds and to enh~nre grease removal
p~lrOI.l~.
Various detersive ingredients employed in the present co.~pos~;ons optionally can be
30 further stabilized by absoll,mg said i~l~dic.~ onto a porous hydrophobic substrate, then
coating said substrate with a hyd~ ,hobic coating. Preferably, the detersive ingredient is
a~1miYed with a surfactant before being absorbed into the porous ~ul~ te. In use, the
detersive i~l~die.ll is .~leased from the substrate into the a~ons washing liquor, where it
pe.ro~ s its int~n3ed detersive fimrtjon
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To illustrate this techniq-le in more detail, a porous hydrophobic silica (tr;~emqrk
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~inin~ 3%-
5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the
c.~lne/surfactant solution is 2.5 X the weight of silica. The resl~ltin~ powder is dijl,el~ed
5 with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can
be used). The res~lltin silicone oil di~el~ion is em~lcifi~od or otherwise added to the final
dete.ge,ll matrix. By this means, ingredients such as the afole.... ~lioned enzymes,
bleaches. bleach activators, bleach catalysts, photoactivators, dyes, lluolesc~"~, fabric
conditioners and hydrolyzable ~ul r.~ tc can be "p~ot~,c~,d" for use in dct.lgellts,
10 in~lu~lin~ liquid laundry det~l~gel~l colll~osilions.
Liquid d~l.,lg.,ln colllpos;l;~ c can contain water and other solvents as Cdlli.,l~. Low
molecular weight primary or secondary alcohols exemplified by ...~ ol, ethanol,
I,rop~ol, and isopr~l,~,ol are suitable. Monohydric alcohols are p~fell~ for solubilizing
15 sulra~ t, but polyols such as those cont~inir~ from 2 to 6 carbon atoms and from 2 to 6
hydroxy groups (e.g., 1,3-pro~ iol, ethylene glycol, glycerine, and 1,2-prop~-~iol)
can also be used. The co,upo~i~;orl~ may contain from 5% to 90%, typically 10% to 50%
of such carriers.
20 The det~ ,~ cou~po~ nc herein will preferably be forrml1~d such that, during use in
a(ll)eollC cle~ning opelaliolls, the wash water will have a pH of between 6.5 and 11,
p,~fe.~bly ~ 7.5 and 10.5. Liquid dishwashing product formulations preferably
have a pH ~t~ ,n 6.8 and 9Ø Laundry products are typically at pH 9-11. Tec~lni~lues
for controlling pH at r.~o~ d usage levels include the use of buffers, alkalis, acids,
25 etc., and are well known to those skilled in the art.
Granules ~ re
Adding the bis-alkoxylated cationics of this invention into a clulchcl mix, followed by
30 col~ lional spray drying, helps remove any residual, I,oterltially malodorous, short-chain
amine co~ lc. In the event the formulator wishes to pl.,pale an ~miY~ble particle
cont~ini~ the aL~oxylated c~l;o.~irs for use in, for example, a high density granular
de~r~nl, it is l,l.,f,.led that the particle composition not be highly ~Ik~lin~o. Processes for
piCp~i~lg high density (above 650 g/l) granules are desclibed in U.S. Patent 5,366,652.
35 Such particles may be form~ d to have an effective pH in-use of 9, or below, to avoid
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the odor of in,lJu-ily amines. This can be achieved by adding a small ~mo~nt of acidity
source such as boric acid, citric acid, or the like. or an a~ ol,liate pH buffer, to the
particle. In an alternate mode, the prospective problems associated with amine malodors
can be m~c~d by use of perfwne ingredients, as disclosed herein.
Examples
The following examples are illustrative of the present invention, but are not meant to limit
or otherwise define its scope. All parts, ~ ges and ratios used herein are e~r~ssed
10 as ~ent weight unless otherwise specified.
In the following examples, the abbreviated component i-le~-~;r.r-lions have the following
,..P~ni~e.~
LAS : So~ m linear C12 aL~cyl b~ n~ sulfonate
TAS : Sodil~m tallow allcyl sulfate
C45AS : So~ m C14-C1s linear alkyl sulfate
CxyEzS : .Sodi~m Clx-C1y bl~lched alkyl sulfate
co--A~ ~e~ with z moles of ethylene oxide
C4SE7 : AC14 15 predo.. ~in~tly linearprimary
alcohol co~-A~ ed with an average of 7 moles
of ethylene oxide
C25E3 : A C12 15 branched primary alcohol
co.-A~n~ed with an average of 3 moles of
ethylene oxide
C25E5 : A C12 15 ~l~ched primary alcohol
conAPnc~Pd with an average of 5 moles of
ethylene oxide
CocoEO2 : Rl.N+(cH3)(c2H4oH)2 with Rl = C12 ~
C14
Soap : Sodium linear alkyl carboxylate derived from
an 80/20 mi~lule of tallow and coconut oils.
TFAA : C16-C18 alkyl N-methyl glllc~miA~P
TPKFA : C12-C14 topped whole cut fatty acids
STPP : Anhydrous sodium tripolyphosphate
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Zeolite A : Hydrated Sodium ~ minosilicate of forrnula
Nal2(A1~2Si~2)12- 27H20 having a primary
particle size in the range from 0.1 to 10
NaSKS-6 : Crystalline layered silicate offonnula
~ -Na2Si20S
Citric acid : A~ dlous citric acid
Carbonate : Anhydrous sodium calbol~t. with a particle
size
~ 200~1m and 900~1m
BicalL,unate : Anhydrous sodium bicarbonate with a particle
size di~llibulion ~l..__n 400~1m and 1200~m
Silicate : Amorphous SoAil~m Silicate (SiO2:Na2O; 2.0
ratio)
Sodium sulfate : Anhydrous sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size dis~ ion ~t~ ,n
425~1m and 850 llm
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average molecular weight 70,000.
CMC : So li~m carboxymethyl ce~ lose
d5e : Proteolytic C~ 111_ of activity 4KNPU/g sold
by NOVO Ind~ if s A/S under the tradf~ n~
Savinase
Alcalase : Proteolytic e.~llle of activity 3AU/g sold by
NOVO L~llif s A/S
Cçlll.lsc.... : Cellulytic c.lL~llle of activity 1000 CEVU/g
sold by NOVO IJ~ ies A/S under the
tra(lf~ .. r Carezyme
Amylase : Amylolytic enzyme of activity 60KNU/g sold
by NOVO Industries A/S under the ~ f n-.nr
Tennamyl 60T
Lipase : Lipolytic el~llle of activity 100kLU/g sold
by Lipolase
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Endolase : Endoglunase enzyme of activity 3000
CEVU/g sold by NOVO Industries A/S
PB4 : Sodium pe,bG,~te te~rahydrate of nominal
formula NaBo2.3H2o-H2o2
PB1 : Anhydrous sodium perborate bleach of
nominql formula NaBo2.H2o2
Pe..,all,ollate : Sodium r~rc~l~O~IA~ of nominal formula
2Na2C03 3H2~2
NOBS : Nonanoylo~yl~ sulfonate int_e formof
the sodium salt.
TAED : Tetraacetylethyk.-P~ .. inP
DTPMP : Diethylene ~ e penta (methyhne
phosphon~~), llla~ d by Monsanto under
the Trade name Dequest 2060
Photoactivated bleach: Sulro.~t~d Zinc Phthaloc~rani~ ell~a~ t~
in bleach dextrin soluble polymer
Bri~l~lfner 1 : Di~o~ m4,4'-bis(2-sulphostyryl)biph~,~l
13l igl~ 2 : Disodium 4,4'-bis(4-anilino~-morpholino-
1.3.5-triazin-2-yl)amino) stilbene-2:2'-
disulfonate.
HEDP : 1,1-hydro~yelllane dil,hosl,honic acid
PVNO : Polyvi~ll,yridine N-oxide
PVPVI : Copolymer of polyvinylpyrrolidone and
vinyli..~ ole
SRA 1 : SulÇobe~o~l end capped esters with
oxyethylene oxy and t~ hll.~loyl bacl~l~n~
SRA 2 : Diethoxylated poly (1, 2 propylene
lele~hll,alate) short block polymer
Silicone aJ liroa~.l: Polydimethylsiloxane foam controller with
~ilo~r~nP-oxyaLkylene copolymer as di~ g
agent with a ratio of said foam controller to
said di~ sing agent of 10:1 to 100:1.
In the following Examples all levels are quoted as % by weight of the composition.
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EXAMPLE I
The following d~tergent formulations according to the present invention are ~re~aled,
where A and C are phosphorus-cont~inin~ del~ rge.lt compositions and B is a zeolite-
cont~ininp dele.ge.lt composition.
B C
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45AS 8.0 5.0 11.0
MA/AA- 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 1.5
CocoMeEO2~ 1.5 1.0 2.0
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Bri~h~r.~r 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone a~liro~.l 0.3 0.3 0.3
F~.ru.l~e 0.3 0.3 0 3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 - 4.0 10.0
PB1 4.0 0
~ICa~ 18.0 18.0 21.0
TAED 3.0 3.0
Photo~rtivated bleach 0.05 0.05 0.05
aSC 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
sodium sulfate 3.0 3.0 5.0
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R~l~n-~e (Moisture &
Miscellaneous) To: 100.0 100.0 100.0
Densi~y (g/litre) 630 670 670
*The bis-AQA-l (CocoMeEO2) surfactant of the Example may be replaced by an
5 equivalent amount of any of surfact~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~t~nt~ herein.
EXAMPLE II
The following dete.~ t form~lqtions, according to the present invention are
10 ~ alC~:
D E F
Zeolite A 30.0 22.0 6.0
Sodium sulfate 19.0 5.0 7.0
MA/AA 3.0 3.0 6.0
LAS 13.01 1 .0 21 .0
C45AS 8.0 7.0 7.0
CocoMeEO2* 1.0 1.0 1.0
Silicate - 1.0 5.0
Soap - - 2.0
Bri~ht~n~r 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
DTPMP - 0.4 0.4
C45E7 1.0 1.0 1.0
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Arnylase 0.1 0.1 0.1
Ce~ lq~e 0.1 0.1 0.1
NOBS - 6.1 4.5
PB1 - 2.0 4.1
Pl.. ~o~ ated bleach 1.05 0.5 0.2
Sodium sulfate - 6.0
n~e (Moisture
& ~ cell~nPous) To: 100 100 100
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*The bis-AQA-l (CocoMeEO2) surfactant of the Example may be replaced by an
equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfactants herein.
EXAMPLE m
The following high density dete~gellt formulations, according to the p~esent
invention are ple~ d:
G H
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3 0 3 0
CocoMeEO2~ 1.0 1.5 1.5
DTPMP 0.4 0.4 0.4
CMC 04 04 04
MA/AA 4.0 2.0 2.0
Agglo~ al~:S
LAS 5.0 5 0 5 0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Call,Gnate 8.0 8.0 4.0
Spray On
E~-ru~e 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicdl~lLat~ - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PBl - 2.0 3.6
Photoactivated bleach 1.0 0.75 0.5
Polyethylene oxide
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of MW 5,000,000 - - 0.2
Bentonite clay - - 10.0
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0 4
Amylase 0.6 0.6 0.6
Ce~ e 0.6 0.6 0.6
Silicone a~ltifo~ll 5.0 5.0 5 0
Dry additives
Soli~m sulfate 0.0 3.0 0.0
R~l~n~e (Moisture &
~i~cell~n~ous) To:100.0 100.0 100.0
Density (g/litre) 850 850 850
*The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be ~placed by an
15 equivalent amount of any of slll r~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
~ulr~el; ..l~ herein.
EXAMPLE IV
20 The following high density dete.~ t formulations according to the present invention are
d:
M N
Blown Powder
Zeolite A 2.5 2.5
So~ m sulfate 1.0 1.0
Coc~o~r-r.02~ 1.5 1.5
om~orate
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DTPMP 0.4 0 4
Spray On
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C2SE5 5 0 5 0
~.ru~ O
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
PB1 8.0 15.0
Photoactivated bleach 0.27 0.8
SRA 1 0.3 0.3
~ot~ase 1.4 1.4
Lipase 0.4 0.4
Cellul. se 0.6 0.6
Amylase 0.6 0.6
Silicone ~,tiroaLu 5.0 5.0
igl.l~ nf- 1 0.2 0.2
Brigh~nPr 2 0.2
Rqlqn~e (Moisture &
~Siccellqn~ool~c) To: 100 100
Density (g/litre) 850 850
*The bis-AQA-l (CocoMeEO2) ~Çhc~lt of the Ex. mple may be replaced by an
equivalent ~mount of any of ~"~ r ~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
~ulr; ~r~"1~ herein.
EXAMPLE V
The following hand w. sh d~bc~g~ form~lq~ion~ acco~i,lg to the present invention, are
d by mi~cing the ingre~ie,l~ tGg~ r in tne ~lcelllage weight 5'~1U~ as in~irq-
~below.
A B C D
LAS 15.0 12.0 15.0 12.0
TFAA 1.0 2.0 1.0 2.0
C25E5 4.0 2.0 4.0 2.0
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AQA-9* 2.0 3.0 3.0 2.0
STPP 25.0 25.0 15.0 15.0
MA/AA 3.0 3.0 3.0 3.0
CMC 0.4 0.4 0.4 0 4
DTPMP 1.0 1.6 1.6 1.6
Cal~n~t~ 2.0 2.0 5.0 5.0
Bic~l~olLa~e - - 2.0 2.0
Silicate 7.0 7.0 7.0 7.0
~o~a3e 1.0 - 1.0 1.0
Amylase 0.4 0.4 0.4
Lipase 0.12 0.12 - 0.12
Pl-o~o~cl;vated bleach 0.3 0.3 0.3 0.3
Sulfate 2.2 2.2 2.2 2.2
PB1 4.0 5.4 4.0 2.3
NOBS 2.6 3.1 2.5 1.7
SRA 1 0.3 0.3 0.7 0.3
Brigl~r~ ~f ~ 1 0.15 0.15 0.15 0.15
Rqlqnre misc./water 100.0 100.0 100.0 100.0
to 100
AQA-~; May be replaced by any AQA ~u~rac~ described herein. ~f,.led AQAsurf: ~tq-nts for use in this example are those with from 10 to 15 ethoxy groups; for example
AQA-10, AQA-16.
s
The for~go~ Examples illustrate the present invention as it relates to fabric laullde.illg
colllpo~ but are not ;~.t. ~ d to be limitin thereof.
EXAMPLE VI
The following illustrates ll~ Ules of bis-AQA surfactants which can be ~lb~ te~ for the
bis-AQA s~r~e~ listed in any of the folegoilg E~ les. As disclosed hereinabove,
such I~ lu~.,s can be used to provide a ~ Ull of ~hlrullllallce bcnff.l~ and/or to provide
cle~ning compositions which are useful over a wide variety of usage conditions.
is Preferably, the bis-AQA surf~ ntc in such mixtures differ by at least 1.5, preferably 2.5-
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20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-
limiting examples of such lni~lulcs are as follows.
Components Ratio (~,vt.)
bis-AQA-l + bis-AQA-5 1:1
bis-AQA-1 + bis-AQA-10 1:1
bis-AQA-1 + bis-AQA-15 1:2
bis-AQA-1 + bis-AQA-5
+ bis-AQA-20 1:1:1
bis-AQA-2 + bis-AQA-5 3:1
bis-AQA-5 + bis-AQA-15 1.5:1
bis-AQA-1 + bis-AQA-20 1:3
Mixtures of the bis-AQA ~ulr ~ i herein with the co..~iponding cationic ~ulr~ 1cwhich contain only a single ethoxylated chain can also be used. Thus, for eY- . 'e,
15 ~ Lul_S of ethoxylated cationic aulr~ of the formula RlN+CH31EO]x[EO]yX~ and
R1N+(CH3)2[EO]zX-~ wLe.~,~ Rl and X are as ~licclose-l above and Wll,;~l one of the
cationics has (x+y) or z in the range 1-5 preferably 1-2 and the other h_s (x+y) or z in the
range 3-100, preferably 1~20, most pre&rably 14-16, can be used herein. Such
colllposil;onC advantageously provide ill~)~'OVed dc~.g~ pelrulll.ance (especi~lly in a
20 fabric l~und. .u~g context) over a bloader range of water hal:llleSS than do the cationic
~ulr~r~ herein used individually. It has now been discovered th_t shorter EO c~tionics
(e.g., EO2) ill~.o-e the clP~ ~.rull.-a lce of anionic s~llr~ in soft water, ~he~as
higher EO cationics (e.g., EO15) act to improve hardness tolerance of anioniC surfa~t~n~c,
thereby improving the ck~ pc.rulmar.ce of anionic sulrac~lls in hard water.
25 Co..~Y-~ ;on~l wisdo~ in the d~,t,.ge~y art suggests that builders can olJti l~ze the
pc.Çolll~ce "wi-do~." of anionic surf~ ntc. Until now, however, bro~ning the
wil~dow to ~ l~O"~p~c~ e~ lly all conditions of water ha~dl1ess has been i l-~ossil~le to
achie~e.
30 The laundry dete.ge.ll colll~osilioils p-epaled using one or more Çol~,going COIlllill~liOnS of
i~ledien~ can optionally be built with any non-pho~l)hate or phosphate builders, or
l..S thereof, typically at levels of from 5 % to 70%, by weight of finich~l
C~ )OSilioll.
EXAMPLE VII
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The following illustrates mixtures of conventional non-AQA surfactants which can be used
in combination with the bis-AQA surfact~ntc in any of the foregoing Examples, but is not
int~nll~od to be limiti~ thereof. The ratios of non-AQA sulr~rl~nl~i in the nli}~lu~s are
S noted in parts by weight of the ~ racLdlll mixtures.
Mixtures A-C
In~l.,di~ Ratios
AS*/LAS 1: 1
AS/LAS 10:1 (pref. 4:1)
AS/LAS 1:10 (pref. 1:4)
*In the fo.~,going, the plilllary~ s--b~ lly linear AS surfactant can be let,laced by an
equivalent A.llO~ of seco~ AS or branched-chain AS, oleyl sulfate, and/or miAIUI~S
thereof, in~lu~ ul~,s with linear, primary AS as shown above. The "tallow" chainlS length AS is particularly useful under hot water co~ ;on~ up to the boil. "Cocon!~tn AS
is l,lef,-l~d for cooler wash ~ ules.
The Illi~lules of alkyl sulfate/anionic surf~t~nt~ noted above are moAifi~d by illCOl~lalillg
a nonionic non-AQA surfactant therein at a weight ratio of anionic (total) to nonionic in the
range of 25:1 to 1:5. The nonionic ~ulra~ can colll~ e any of the conventional classes
of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid
amides (less l)lcf .le~ if LAS is present), or nnA~ s thereof, such as those disclosed
hereinabove.
Mixtures D-F
AS*/AES 1:1
AS/AES 10:1 (pref. 4:1)
AS/AES 1:10 (pref. 1:4)
*Can be replaced by s~-o~ y, ~.a,~ched or oleyl AS as noted above.
30 The Il~L~lUl~,s of AS/AES noted above can be modified by ulCOl~OIdlillg LAS therein at a
weight ratio of AS/AES (total) to LAS in the range from 1:10 to 10:1.
The ll~lures of AS/AES or their reslllti~ AS/AES/LAS nlixLules can also be colllbil ed
with nonionic surfactants as noted for Mixtures A-C at weight ratios of anionic (total) to
nolliol~ic in the range of 25:1 to 1:5.
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Any of the foregoing mixtures can be modified by the incorporation therein of an amine
oxide surfactant, wherein the amine oxide comprises from 1% to 50 % of the totalsurfactant mixture.
Highly ~ . d co"lbinations of the fo,egoil g non-AQA surf: ~t~ntc will co",~,ise from
3% to 60%, by weight of the total fini~h~d laundry deterg_nt composition. The finich.od
culllposilions will l.,ef, .ably co",~,ise from 0.25% to 3.5%, by weight of the bis-AQA
~r~ t.
