Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITION
Te~h~-;c~l Field
S
The present invention relates to a deler~,ent co-1-posilion compricing a peroxygen
bleach, a bleach catalyst a non-AQA s~lrf~r-t~nt and a bis-alkoxylated qua~e
ammonium ~bis-AQA) c~tio~i~ surfactant.
R~ .nd ~o the Invention
The formulation of laundry det~ ,enls and other cl~nin~ co---pos;lions ~l~e~ a
conci-lP-~hle ~'h~llPngP, sinc~ modern c~"-po~,ilions are required to remove a variety of
soils and stains from diverse substrates. Thus, laundry det~ , hard surface
15 ~lP~nPrs, ch~mI)oos and other ~nal cl~n~ P colnposi~;onc~ hand dishwashing
dele.~,enLs and dete1~,ent compositions suitable for use in ?~ v.~ ;C disl,w~sl,c;.~ all
require the proper sPl~tis)~ and co",binalion of ingredients in order to function
effectively. In ge~ P-~l, such del~.gelll co...~s;l;onc will contain one or more types of
surf~-t~ntc which are ~1~Pci~n~Pd to loosen and remove dirre~nl types of soils and stains.
20 While a review of the lite.~u~ would seem to in~ tP that a wide sPl~tic)n oiFsurf~t~ntc and surfactant co"~binalions are available to the d~ ,ent m~mlf~ rer, ~e
reality is that many such ingredients are cpeci~lty ch~.mjr~l.c which are not suitable in
low unit cost items such as home-use laundry dete;~enls. The fact remains that most
such home-use products such as laundry deLelge.,t~ still mainly comprise one or more of
25 the convention~l ellluAylat~d noninnir and/or s ~lfZ~t~d or sulfonated anionic S~1 r~
~ u111ably due to ec~nomic con~ ;ons and the need to formulate co~ ~s;l;ons
which function ~ ly well with a variety of soils and stains and a variety offabrics.
30 The quick and effi~ nt removal of dirl~e-~l types of soils and stains such as body soils,
greasy/oily soils and certain food stains, can be probl~m~ic. Such soils comprise a
11liAIUl~ of hydrophobic t~iglycericles, lipids, complex poly~ch~rides, ino,E;anic salts
and protein~C~Qus matter and are thus notoriously difficult to remove. Low levels of
hyd1ullhobic soils and residual stains often remain on the surface of the fabric after
35 washing. Successive washing and wearing coupled with limited hydrophobic soil removal
in the wash cumlin~tes in a build up of residual soil and stain which further entraps
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particluate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy
appearance which is perceived as unwearable and discarded by the col~ulller.
The literature suggests that various nitrogen-cont~ining cationic surf~t~ntc would be useful
5 in a variety of cleaning compositions. Such materials, typically in the form of amino-,
amido-, or quatemalr ammonium or imif~ olinium compounds, are often deci~n.o~l for
specialty use. For example, various amino and quaternary ammonium surfactants have
been suggested for use in shampoo compositions and are said to provide cocm~ti~ be~
to hair. Other nitrogen-cont~inin~ surf~t~nt~ are used in some laundry de~ .lLs to
10 provide a fabric SO~ g and anti-static benefit. For the most part, however, the
co...~ ~ial use of such materials has been limited by the ~iffir111ty encou~ cd in the large
scale m~mlf~ re of such compounds. An additional lirnitation has been the potential
precip~tion of anionic active colnL)ollcll~, of the deL~.ge.lL composition occasioned by their
ionic interaction with cationic surf~t~ntc. The aforementioned nonionic and anionic
15 ~ulr~ remain the maior ~,ulr~cL~L components in today's laundry compositi-)nc
It has now been discovered that certain bis-alkoxylated 4u~t~ aly ammonium (bis-AQA)
colll~uullds can be used in various delLI~ellL compositions to boost d~t~g~,.l;y ~r~ lce
on a variety of soil and stain types, particularly the hydrophobic soil types, cc ~ lollly
20 encountered. Unexpectedly, it has now been discovered that compositions co-~ g bis-
AQA surf~ct~ntc, peroxygen bleach and a metal-cont~ining bleach catalyst deliver superior
c1e~ning and w1.;~ P-cs ~u~ ce versus products c~ ;..;n~ the technologies alone.
The bis-AQA ~,ulr~ A~, of the present invention provide ~,~sl;.-.l;~1 benefits to ~e
25 for~m~1~tor, over CAI;~ ' surf~rf~ntc previously known. For example, ~e bis-AQA
surfactants used herein provide n ~rkt~(1 impro~enlc:lll in cl~nin~ of "e~ greasy/oily
lly~hvyhobic soils regularly encw~ r~. Moreover, ~e bis-AQA surf~t~ntc are
colllyalil)le with anionic ~u~ ntc commonly used in de~ compositions such as aLkyl
sulfate and aLIcyl l~l~ze.le sulfonate; incompatability with anionic eol~onellL~ of the
30 dctelg~ composition has commonly been the li...i~ g factor in the use of c~tionir
surfactants previously known. Low levels (as low as 3 ppm in the laundering liquor) of
bis-AQA surf~ t~ntc gives rise to the benefits described herein. Bis-AQA su~f~rt~ntc can
be form~ ted over a broad pH range from 5 to 12. The bis-AQA :iUll~CI;1lllx can be
p~ d as 30% (wt.) solutions which are pumpable, and ~ Ol., easy to handle in a
3~ m~m1f~ctl1ring plant. Bis-AQA :~ull;~ with degrees of ethoxylation above 5 are
_
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sometimes present in a liquid form and can Lll~icfole be provided as 100% neat rnaterials.
In addition to their beneficial h~n~lling plu~ellies, the availability of bis-AQA surfactants as
highly concentrated solutions provides a sl-bst~ntiAl economic advantage in transportation
costs. The bis-AQA surfart~nt~ are also cnlnpAtible with various ~ fullle ingredients,
S unlike some cationic surfA~t~nt~ known in ~e art.
Bleach catalysts (characterized by the presence of at least one transition metal atom)
hllelacL with peroxide b~eaellin~ species to form very powerful hydrophilic bleArll~os.
These bleaches deliver strong b ellerlLs on colored hydrophilic stains and hydlul)l~ilic
10 e~e.~ddy soils (i.e., socks). Historical use of bleach catalysts was made ~1im~ult bec~ùse
of conrern~ r~ga~ fabric damage. It has now been found that fabric damage caused by
using a ~ se catalyst, known to cause fabric tl~m~e, can be much reduced when
the d~L~ llL composition conl~lisi~s a bis-AQA cationic ~ulra~;L~IlL. It is proposed that
these cationics adsorb onto fabrics, motlifin~ the surface charge of the fabric and
15 ~otelltially ion-pairing with the acli~.tt d catalyst to ..,;..;...i,~ or prevent fabric damage.
It is believed that the greasy/oily soils are effectively solubilized by bis-AQA, Lll~lcl,y
allowing access of the hydrophilic catalyst bleach to the colour bodies in the soil (e.g.
c~lLlalJ~ed pi~m~nt.c) resl~lting in improved soil decolouration. The ability of the
20 compositions described herein to clean both hydrophilic and hydophobic soils results in
~u~lior cle~nin~ and wl.i~ c~ mAi..t. ,~A~re
und Art
U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. I,oprest, relates
to anionic/r~tionir ~ulr~L n~iALul s. U.K. 2,040,990, issued 3 Sept., 1980, to A. P.
Murphy, R.J.M. Srnith and M. P. Brooks, relates to ethoxylated c~tioni~s in laundry
dt;l~,~geul~.
S~ y ofthe Invention
~ The present invention provides a composition comprising or prepared by c~ bi,~ing a
peroxygen bleach, a bleach catalyst a non-AQA surfactant and an effel;~ivt; amount of a bis-
al~oxylated ~luat~ / ammonium (bis-AQA) cationic surfactant of the formula:
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R~ /AP X--
R2/ AqR
Whclcll~ Rl iS a linear, branced or substihlt.o~ Cg-Clg aLkyl, aL~cenyl, aryl, aLkaryl, ether or
glycityl ether moiety, R2 is a Cl-C3 alkyl moiety, R3 and R4 can vary in-lepen-lPntly and are
5 selected from hydrogen, methyl and ethyl, X is an anion, and A and A' can varyindependently and are each Cl-C4 alkoxy, p and q can vary indepen~1~ntly and are hllc~ crs of
from 1 to 30.
D~ D~r_l ,uti~ n of the Invention
Pçroxygen Ble~cilin~ Agent
The dc~gcllL compositions herein c~ll~lise a peroxygen blea~ agent. Such b~ chir~
agents are typically present at levels of from 1% to 30%, more typically from 5% to 20%,
of the dclcUgc~lL composition, especi~lly for fabric laundering.
Plcrel-~d peroxygen bleaches are perhydrate bleaches. The perhydrate bleach is normally
il~col~ulaled in the form of the perhydrate salt, especially the sodium salt, at a level of
from 1% to 40% by weight, more ~lcr~lably from 2% to 30% by weight and most
preferably from 5 % to 25 % by weight of the compositions.
Although the p~.hydlale bleach itself has some bleaclling capability, a su~- liul bleach
exists in the peracid formed as a product of the reaction between the hydrogen peroxide
released by the ptlllydl~Lc and a bleach acLi~a~o~ cÇol.llcd peracids are also envisaged as
a ~lef~llcd pelu~y~ell blraching species.
Examples of suitable perhydrate salts include perborate, ~l.;~l,onate, perphosphate,
persulfate and persilicate salts. The ~cr~.led perhydrate salts are normally the aLIcali metal
salts. The ~,llydl~tc salt may be inrl~l-le~l as the crystalline solid without additional
~lo~cLion. For certain perhydrate salts however, the ~lcrc~lcd executiûns ûf such granu}ar
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compositions utilize a coated form of the material which provides better storage stability
for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula NaBO2H2O2
or the tetrahydrate NaBO2H2O2.3H2O.
ALkali metal percarbonates, particularly sodium percarbonate are p~ .,d perhydrates for
inrl~ iQn in compositions in accordance with the invention. ~so~ lm ~elcall,ol~ate is an
addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available
colllmel.;ially as a crystalline solid. Sodium pel-;all~onate, being a hydrogen peroxide
addition co,l,l)uu,1d tends on dissolution to release the hydrogen peroxide ~uite rapidly
which can increase the tçntl~n-~y for loc~ e~l high bleach concellLldtions to arise. The
pcl~albo~ L is most preferably incolpo,aLed into such compositions in a coated form
which provides in-product stability.
A suitable coating material providing in product stability colllplises mixed salt of a water
soluble aLkali metal sulphate and c~bollale. Such co~ting~ together with coating processes
have previously been desclilJcd in GB-1,466,799, granted to Interox on 9th March 1977.
The weight ratio of the mixed salt coating material to ~ ;a bonate lies in the range from 1
: 200 to 1: 4, more ~lc;Ç~ably from 1: 99 to 1: 9, and most p lcÇ~,.dbly from 1: 49 to 1:
19. Preferably, the mixed salt is of sodium sulrh~te and sodium CalLOl~ale which has the
general formula Na2SO4.n.Na2CO3 wlle~ 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 co~tin~ which contain silicate (alone or with borate salts or boric acids or other
inol2~d~ics), waxes, oils, fatty soaps can also be used advantageously within the present
invention.
A preferred ~,e.~;a.l,ondte bleach colll~lises dry particles having an average particle size in
the range from 500 llliclullleters to 1,000 micro,l,~Lers, not more than 10% by weight of
said particles being smaller than 200 ll~icrollleters and not more than 10% by weight of said
~ particles being larger than 1,250 micl~l,.,t~
Another suitable ble~ching agent which can be used without r~ ;lion enco...~ ses35 percarboxylic acid ble~chin~ agents and salts thereof. Suitable examples of this class of
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agents include m~gn~sium monoperoxyphth~l~t~ hexahydrate, the magnesium salt of meta-
chloro perbenzoic acid, 4-nonylamino4-oxoperoxybutyric acid and diperoxydo~ler~ne~i- ic
acid. Such bie~hin~ agents are disclosed in U.S. Patent 4,483,781, Hartman, issued
November 20, 1984, U.S. Patent Application 740,446, Burns et al, hled June 3, 1985,
European Patent Application 0,133,354, Banks et al, published re~ualy 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly plercll~d
blea~hing agents also include 6-nonylamino-6-oxopero~yc~lJ,oic acid as described in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al. Potassium pero~y,llono~ lfate
is another inorganic perhydrate salt of utility in the compositions herein.
Mixtures of ble~rlling agents are also envisaged.
Bleach Catalvst
15 The dch.~cllL compositions desclil,ed herein co,l,p,ise as an e~ l component a bleach
catalyst. The catalysts are cs-lnm( nly present in e~ l"ely low levels in product, preferably
from 0.001 % to 5 % by weight, more plere lably from 0.01 % to 2%, most preferably from
0.05% to 1%. Preferably the bleach catalyst is a metal-cont~inin~, more preferably a transition
metal-cont~inin~ bleach catalyst. The ~l~,fcllcd transition metal~o..l;~ bleach catalysts are
20 ...~l~g~ sc or cobalt-cont~inin~ bleach catalysts.
A suitable type of bleach catalyst is a catalyst con,l)~isil~g a heavy metal cation of defined
bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or
no bleach catalytic activity, such as zinc or ~ .. cations, and a seql~estrant having defined
25 stability cs.~ .lc for the catalytic and auxiiiary metal cations, particularly
ethyl~ ;..- t~ aac~lic acid, ethyle~ r.~ a (methylenephosphonic acid) and water-
soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.
P~,rclled t~rpes of bleach catalysts include the ...~ se-based complexes disclosed in U.S.
Pat. 5,246,621 and U.S. Pat. 5,244,594. I~cr~,~rcd examples of these catalysts include
MnIV2(u-0)3(1,4,7-L~Ic~,yl-1,4,7-triazacyclononane)2-(PF6)2, Mnm2(u-O)l(u-
OAc)2(1,4,7-Llill,~Lllyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-0)6(1,4,7-
Llia acyclononane)4-(C104)2, MnmMnIV4(u-O)l(u-OAc)2 (1,4,7-LlilncLl~yl-1,4,7-
triazacyclonol~,e)2-(ClO4)3, and ~ Lures thereof. Others are described in Eulo~call patent
application public~tion no. ~49,272. Other ligands suitable for use herein include 1,~,9-
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trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-
triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful in the compositions herein may also be selected as apll.~,iale for
the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and
U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear ~ kse
(IV) complexes such as Mn(l~4~7-trimethyl-l~4~7-lli3zacyclononane)(ocH3)3-(pF63.
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble
10 complex of m~ng~n~se (III), and/or (IV) with a ligand which is a non~arboxylate polyhydroxy
co.~,puund having at least three co~se~;uli~e C-OH groups. ~,r~ ,d ligands include sorbitol,
iditol, dulsitol, ~-.~ ol, xylithol, arabitol, adonitol, meso e.yllllilol, meso-inositol, lactose,
and llli~Lules thereof.
15 U.S. Pat. 5,114,611 teaches a bleach catalyst co~ isin~ a complex of transition metals,
inr!~ ng Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the
forrnula:
R2 R3
R1_N=C-B-C=N-R4
W11C1CL1I Rl, R2, R3, and R4 can each be selPcte(l from H, substituted aLkyl and ary} groups
such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered ring. Said ring can
further be sub~ d. B is a bridging group se!ected from O, S. CR5R6, NR7 and C=O,wl~.ein R5, R6, and R7 can each be H, aLkyl, or aryl groups, inr~ iin~ s~ sl or
25 ~ d groups. Preferred ligands include pyridine, pyridazine, pyrimi-linP, ~yla~ille,
imi~1~7 )1e, pyrazole, and triazole rings. Optionally, said rings may be ~lb~ rd with
subst~ nt~ such as alkyl, aryl, aLkoxy, halide, and nitro. Particularly ~rer~L.~,d is the ligand
2,2'-bispyridylamine. ~f~,Ll~,d bleach catalysts include Co, Cu, Mn, Fe,-bi~y,idyl..-eth~n~
and -bispyridylamine complexes. Highly ~lcrt~lcd catalysts include Co(2,2'-
30 bispyridylamine)C12, Di(isothiocyanato)bispyridylamine~obalt (II), trisdipyridylamine-
cobaltaI) perchlorate, Co(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridyl~i"e) copper(II)
perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and ~ ulcs thereof.
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Plcf~ d examples include binuclear Mn complexes with tetra-N-dentate and bi-N-dentate
ligands, including N4Mn~ u-O)2MnIVN4)+and [Bipy2MnIII(u-O)2MnIVbipy23-(ClO4)3.
While the structures of the bleach-catalyzing mAngAn~se complexes of the present invention
S have not been elucidated, it may be spec~ t~l that they comL,lise chelates or other hydrated
coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of
the ligand with the m~ng~nPse cation. Likewise, the oxidation state of the m~n~npse cation
during the catalytic process is not known with ce,ldillLy, and may be the (~II), (+m), (+IV)
or (+V) valence state. Due to the ligands' possible six points of ~tf~rhmPnt to the mAng;~n~se
10 cation, it may be reasolldbly specl~l~ted that multi-nuclear species and/or "cage" structures may
exist in the aqueous blP-~ching media. Whatever the form of the active Mn ligand species
which actually exists, it functions in an ~d~ y catalytic ~ to provide improved
ble~hin~ ~el~o~ es on stubborn stains such as tea, k~lçh~ coffee, wine, juice.
15 Other bleach catalysts are described, for example, in European patent application, publication
no. 408,131 (cobalt complex catalysts), El~r~cal~ patent applications, publication nos.
384,503, and 306,089 (metallo-poll,hyl"l catalysts), U.S. 4,728,455 (~A~ Ps~ /ml-lti~n
ligand catalyst), U.S. 4,711,748 and Eul~l patent applir~ti~m, publication no. 224,952,
(absorbed m~r~AnP~e on All~min--silirAt~o catalyst), U.S. 4,601,845 (~ minr)sili~te support
with .. ~A~ ose and zinc or mag,lesiuln salt), U.S. 4,626,373 (.. ~ g~ se/ligand catalyst),
U.S. 4,119,557 (ferric complex catalyst), German Pat. s~ecir.~ ~I;o~ 2,054,019 (cobalt chelant
catalyst) C'~n~ n 866,191 (transition metal-cont~ining salts), U.S. 4,430,243 (ch~!~nt~ with
g,~ se cations and non-catalytic metal cations), and U.S. 4,728,455 ~ se gluconate
catalysts).
Other preferred e~'ss include cobalt (m) catalysts having the formula:
Co[(NH3)nM~mB bT tQqPp] Yy
30 wherein cobalt is in the +3 oxidation state; n is an integer from 0 to 5 (~lc Ç.,ldbly 4 or S; mose
~l~,f~ably S); M' le~r~sents a mono~ont~te ligand; m is an integer from 0 to 5 (preferably 1 or
2; most preferably 1); B' ~ selll~ a bi~ent~t~ ligand; b is an integer from 0 to 2; T'
~,esell~ a tri(1entAte ligand; t is 0 or 1; Q is a tetr~ n~te ligand; q is 0 or 1; P is a
penta~lPntAte ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + Sp = 6; Y is one or more
35 ~l~r~liately select~l eol~nl~ldllions present in a llulll~el y, where y is an integer from 1 tO 3
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(preferably ~ to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-
b~l~nr.ed salt, plcr~llcd Y are selectPd from the group CO~ .g of chloride, nitrate, nitrite,
sulfate, citrate, acetate, carbonate, and combinations thereof; and wl~rehl further at least one
of the coordination sites ~tt~hP~l to the cobalt is labile under ~ o~ di~hwàsl~llg use
S con~lition~ and the rem~ining coordination sites stabilize the cobalt under aulo.llalic
dishwashing conditions such that the reduction potential for cobalt (m) to cobalt (II) under
~lk~Tinf~ conditions is less than about 0.4 volts (plcr~,.dbly less than about 0.2 volts) versus a
normal hydrogen electrode.
10 E~r~,.led cobalt catalysts of this type have the formula:
[C~(NH3)n(M )m] Yy
wlle~ill n is an integer from 3 to 5 (~rerelably 4 or 5; most p~ert;lably 5); M' is a labile
15 coc~ ;g moiety, ~l~lably sel~cted from the group co~ of chlorine, bloll~e,
hydroxide, water, and (when m is greater than 1) coll~ a~ions ~le~of; m is an integer from 1
to 3 (~l~f,lably 1 or 2; most preferably 1); m+n = 6; and Y is an a~ t~ly selPct~
cuu~ lal~ion present in a llulllb.,l y, which is an integer from 1 to 3 (preferably 2 to 3; most
~l~,f. lably 2 when Y is a -1 charged anion), to obtain a charge-~al~nred salt.
The ~ d cobalt catalyst of this type useful herein are cobalt p~ chloride salts
having the formula [Co(NH3)sCIl Yy, and especially [Co(NH3)sCl]C12.
More ~3lef~ ,d are the present invention compositions which utilize cobalt (III) bleach
catalysts having the form~
[Co(NH3)n(M)m(B)bl Ty
where;ll cobalt is in the +3 oX~ tion state; n is 4 or 5 (~l~,~lably 5); M is one or more
ligands cooldindled to the cobalt by one site; m is 0, 1 or 2 (L~,eÇclably l); B is a ligand
~ coo~lih~Led to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n =
~ 6, and when b= 1, then m=0 and n=4; and T is one or more a~r~liatt:ly selected
coun ions present in a nllmher y, where y is an integer to obtain a charge-b~l~nred salt
(preferably y is 1 to 3; most preferably 2 when T is a -1 cha~ d anion); and wllclehl further
said catalyst has a base hydrolysis rate col~L~lL of less than 0.23 M-l s-l (25~C3.
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Pler~ d T are selected from the group collsi~Li-lg of chloride, iodide, I3-, formate, nitrate,
nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF6-, BF4-, B(Ph)4-, phosphate,
phosphite, silicate, tosylate, meth~nPslllfonate~ and combinations thereof. Optionally, T can be
S protonated if more than one anionic group exists in T, e.g., HPo42-, HC03-, H2P04-, etc.
Further, T may be selPct~ from the group col-ci~l;..g of non-traditional Lor~l~ic anions such
as anionic surfactants (e.g., linear alkylbenzene sulÇol~Lcs (LAS), alkyl sulfates (AS),
alkylethoxysulÇ~l~les (AES), etc.) and/or anionic polymers (e.g., polyacrylates,poly.lrc~llacrylates, etc.~.
The M moieties include, but are not limited to, for example, F-, S04-2, NCS-, SCN-, S203-2,
NH3, P043~, and carboxylates (which preferably are mono-carboxylates, but more than one
carboxylate may be present in the moiety as long as the binding to the cobalt is by only one
carboxylate per moiety, in which case the other carboxylate in the M moiety may be
15 protonated or in its salt form). Optionally, M can be protonated if more than one ar~ionic
group exists in M (e.g., HPo42-, HC03-, H2P04-, HOC(O)CH2C(O)O-, etc.) Plcrellcd M
moieties are ~ (r 1 and ul~u~ ulcd Cl-C30 carboxylic acids having the formulas:
RC(O)O-
wherein R is preferably se!-octe~l from the group consisting of hydrogen and Cl-C30
(preferably C1-C1g) unsubslilult;d and ~ub~lilu~cd alkyl, C6-C30 (preferably C6-Clg)
ul~ub~Li~uLed and ~ul)~iLu~ed aryl, and C3-C30 (preferably Cs-Clg) llns~lbs~ ed and
s~ s~ .lrd het~ a,yl, wL~,lcill sllhsti~lent~ are selected from the group co~ g of -NR 3, -
25 NR 4~, -C(O)OR, -OR, -C(O)NR 2, wh~le;ll R is selecte~l from the group co~ g of
llydlo~ and Cl-C6 moieties. Such s~stihlt~d R Ill,rerolc include the moieties -(CH2)nOH
and -(CH2)nNR 4+, whel.,.n n is an integer from 1 to about 16, preferably from about 2 to
about 10, and most preferably from about 2 to about 5.
30 Most plc~lcd M are call,o~ylic acids having the formula above wherei l R is selected from
the group consi~ lg of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 aLtcyl,
and benzyl. Most ~lcf~,.ed R is methyl. Preferred carboxylic acid M moieties include
formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic,
phth~lic, 2-ethylhPY~noic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric,
35 acrylic, aspartic, fumaric, lauric, linoleic, }actic, malic, and especially acetic acid.
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The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic,
succinate, m~lP~te), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine,
beta-alanine, phenyl~l~nin~).
Cobalt b}each catalysts useful herein are known, being described for example along with their
base hydrolysis rates, in M. L. Tobe, "Base ~ydrolysis of Transition-Metal Complexes", Adv.
Inorg. Bioinor,e. Mech.. (1983), 2, pages 1-94. For example, Table 1 at page 17, provides the
base hydrolysis rates (~esign~tlod therein as koH) for cobalt pent~min~o catalysts complexed
with oxalate (koH= 2.5 x 104 M-1 s~~ (25~C)), NCS- (koHC 5.0 x 10~ M-l s-1 (25~C)),
f~L~ t~ ~OH= 5.8 x 104 M-1 s-l (25~C)), and acetate (koH= 9.6 x 104 M-l s-1 (25~C)).
The most pl~r~llcd cobalt catalyst useful herein are cobalt pent~min~ acetate salts having the
formula [Co(NH3)sOAc] Ty~ wll~relll OAc represents an acetate moiety, and especially cobalt
pent~min~ acetate chloride, ~Co(NH3)sOAc]C12; as well as [Co(NH3)~0Ac](OAc)2;
[Co(NH3)sOAc](PF6)2; [Co(NH3)sOAc](SO4); [Co(NH3)sOAc](BF4)2; and
[Co(NH3)sOAc](NO3)2 (herein HPAC").
These cobalt catalysts are readily pi~dl~;d by known procedures, such as taught for example
in the Tobe article hw~,hll~efore and the refeL~ ces cited therein, in U.S. Patent 4,810,410, to
Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 104345; The Sy~ sis and
Ch~a~;leli~lion of ~lor~,~lic Conl~oullds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inor~.
Chem., 18, 1497-1502 (1979); Inorg. Chem.~ 21, 2881-2885 (1982); Inor~. Chem., 18, 2023-
2025 (1979); Inorg. Sy~ , 173-176 (1960); and Journal of Physical Ch~l-~isL~ 56, 22-25
(1952); as well as the sy~ csis e~ s provided hereinafter.
As a practical matter, and not by way of lilllit~tiOtl, the aulo-lldLiC dishwashing
colu~)OSiliOnS and c~ nin~ pl~esses herein can be ~ eted to provide on the order of at
least one pàrt per hundred million of the active bleach catalyst species in the a~ueous
washing m~rli--m, and will preferably provide from about 0.01 ppm to about 25 ppm, more
preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm
to about S ppm, of the bleach catalyst species in the wash liquor. In order to obtain such
- levels in the wash liquor of an automatic dishwashing process, typical duLo,l~Lic
dishwashing compositions herein will COll~ se from about 0.0005% to about 0.2%, more
preferably from about 0.004% to about 0.08%, of bleach catalyst, especially .~ ose or
cobalt catalysts, by weight of the cle~ning compositions.
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13is-Alkoxylated Ouaternary Amrnonium (bis-AOA) Cationic Surfactant
The third ecsenti~l component of the present invention co~ ises an effective amount of a
bis-AQA surfactant of the formula:
S
R~ /A~R
N+ X
R~/ AqR
wh~le.ll Rl is a linear, branched or substituted alkyl, alkenyl, aryl, aLkaryl, ether, glycityl
ether moiety cont~ining from 8 to 18 carbon atoms, plC re.dbly 8 to 16 carbon atoms, most
plert lably from 8 tol4 carbon atoms; R2 is an aLIcyl group cont~ining from 1 to 3 carbon
atoms, preferably methyl; R3 and R4 can vary indepen-lently and are selected from tne
group co..~;~il;..g of hydrogen (pltf~lled~, methyl and ethyl; X~ is an anion such as
chloride, bromide, methyl sulfate, sulfate, sufficient to provide elc~. ;r~l neutrality. A and
A' can vary inrlepenrl.qntly and are each selected from Cl-C4 aL~coxy, especially ethoxy,
propoxy, butoxy and u~ALul'eS thereof; p is from 1 to 30, preferably l to 15, more
preferably 1 to 8, even more preferably 1 to 4 and q is from 1 to 30, preferably 1 to 15,
more preferably 1 to 8, even more preferably 1 to 4. Most ~ ;re.ably both p and q are 1.
Bis-AQA cuulp~ullds wh~.eiu the hyd~ocall,yl sub~iLue.lL Rl is Cg-C~2, especially Cg-
Clo, e~ re the rate of dissolution of laundry granules, es~eri~lly under cold water
conditions, as colu~aled with the higher chain length materials. Accor~lill~;ly, the Cg-~12
bis- AQA ~r,~ A.-Ix may be ~l~f~ d by some form~ tr rs. The levels of the bis-AQA
sur~ct~nt~ used to ~ , fini~hPd l~ulldl~ det~lgellL col.~osilions can range from 0.1 ~ to
5%, typically from 0.45% to 2.5%, by weight. The weight ratio of bis-AQA to
p~,rc~l,olldle 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 "erre~;~ive amount" of the bis-AQA surfactants to
improve the pelro. m~l.re of clP~ning compositions which contain other optional
ingredients. By an "effective amount" of the bis-AQA surf~rt~nt~ herein is meant an
amount which is ~~ffirient to improve, either directionally or ~iglliiirzlllly at the 90%
confirl.on~e level, the pc.fullllallce of the cleaning composition against at least some of the
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target soils and stains. Thus, in a composition whose targets include certain food stains,
the form~ tf r will use sufficient bis-AQA to at least directionally improve cleaning
performance against such stains. Likewise, in a composition whose targets include clay
soil, the formulator will use sufficient bis-AQA to at least directionally improve cle~ning
p~Lro~ ce against such soil.
The bis-AQA surf~t~nt~ may be used in combination with other d~tcl~ive ~ulra.;L~ at
levels which are effective for achieving at least a directional improvement in clP~ning
p~ dnce. In the context of a fabric laundry composition, such "usage levels" can vary
depending not only on the type and scv~.ily of the soils and stains, but also on the wash
water Iclllp~lalulc, the volume of wash water and the type of washing ~ P.
For example, in a top-loading, vertical axis U.S.-type automatic washing m~ inP using 45
to 83 liters of water in the wash bath, a wash cycle of 10 to 14 .~ s and a wash water
telllpelalul, of 10~C to 50~C, it is plcf~.lcd 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~n~l~tPs into an in-~,odu~t
collcellL.alion (wt.) of the bis-AQA surfactant of from 0.1% to 3.2%, preferably 0.3% to
1.5 %, for a heavy-duty licluid laundry dele~5e.l~. On the basis of usage rates of from 60 g
to 95 g per wash load, for dense ("compact") granular l~ ld~ y det~"gellL~ (density above
650 g/l) this tr~n~l~tes into an in-product concellL.aLion (wt.) of the bis-AQA ~ulrd~;Lall~ of
from 0.2% to 5.0%, plef~"ably 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
tr~n~l~t~s into an in-product cc,.-~e..l . alion (wt.) of the bis-AQA surfactant of from 0.1% to
3.5%, ~n_relably from 0.3% to 1.5%.
3~or example, in a front-lo~i~, ho,i~uuLal-axis Eulc~edll-type alltom~tir wà~hi~lg ~Af'~ ,P
using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 ...i....~c and a
wash water l~lll~,alulc of 30~C to 95~C, it is preferred to include from 13 ppm to
900 ppm, ~ fel~bly from 16 ppm to 390 ppm, of the bis-AQA ~ulrdcLdllL in the wash
liquor. On the basis of usage rates of from 4~ ml to 270 ml per wash load, this tr~n~l~tPs
into an in-product collcelllldlion (wt.) of the bis-AQA sulrdcldll~ of from 0.4% to 2.64%,
preferably 0.55% to 1.1%, for a heavy-duty liquid laundry dcl~l~cu~. On the basis of
usage rates of from 40 g to 210 g per wash load, for dense ("compact") gr~n~ r laundry
dclergc~ (density above 650 g/l) this trancl~tPc into an in-product concentration (wt.) of
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the bis-AQA surfactant 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., "fluffy";
density below 650 g/l), this tr~nCI~t~s into an in-product concentration (wt.) of the bis-
AQA surfactant of from 0.13% to 1.8%, preferably from 0.18% to 0.76%.
Por example, in â top-loading, vertical-axis J~p~nrse-type; ~ o~ r washing m~rhinP
using 26 to 52 liters of water in the wash bath, a wash cycle of 8 to 15 .,~ s and a wash
water tempe.aLul~ of 5~C to 25~C, it is pl. f~red 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
10 basis of usage rates of from 20 ml to 30 ml per wash load, this translates into an in-product
cQ~ .àlion (wt.) of the bis-AQA ~,ulra~ L of from 0.25% to 10%, preferably 1.5% to
2%, for a heavy-duty liquid ld.~ / del.,rgclll. On the basis of usage rates of from 18 g to
35 g per wash load, for dense ("compact") granular laundry det_~gcnLs (density above 650
g/l) this tr~ncl~tes into an in-product col~e~ tion (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~ried granules (i.e., "fluffy"; density below 650 gll), this tr~nc~trs
into an in-product col.cc;-lL alion (wt.) of the bis-AQA ~,ulr~;l~ll of from 0.25% tolO%,
preferably from 0.5% to 1%.
As can be seen from the rOlcgoillg, the amount of bis-AQA surfactant used in a m~rhinr-
wash laundering context can var;y, depending on the habits and practices of the user, the
type of washing m~rllin~, In thiS context, however, one heretofore ul~l~.,iat~d
advantage of the bis-AQA ,l~l r,~ is their ability to provide at least directional
improvements in ~L~ rC over a ~ye~ of soils and stains even when used at
relatively low levels with respect to the ot-h-er ~ul l~ x (generally anionics or
anionic/n->nionir l~ Ul~S) in the fini~hrd compositions. This is to be ~;b~ u;~h.o-l from
other compositions of t_e art wh~,.e.ll various cationic surF~ct~nt~ are used with anionic
surf~ct~nts at or near stoichiometric levels. ID general, in the practice of t'nis invention, the
weight ratio of bis-AQA:anionic surfactant in laundry compositions is in the range from
1:70 to 1:2, plcr~,ldbly from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably 1:15
to 1:8. In laundry compositions which colll~lise both anionic and nonionic surf~ct~nt~, tne
weight ratio of bis-AQ~-mi~d ~nit~nir/nonionic is in the range from 1:80 to 1:2,preferably 1:50 to 1:8.
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Various other cleaning compositions which comprise an anionic surfactant, an optional
nonionic surfactant and specialized surfactants such as betaines, sl~lt~in~s, amine oxides can
also be form~ t~d using an effective amount of the bis-AQA surfAct~nt~ in the manner of
this invention. Such compositions include, but are not limited to, hand dishwashing
S products (ecpec-i~lly liquids or gels), hard surface cleaners, shampoos, personal clc ..-ci.-g
bars, laundry bars, and the like. Since the habits and practices of the users of such
compositions show minim~l variation, it is s~ti~f~rtory to include from about 0.25% to
about 5%, ~l~r~.ably from about 0.45% to about 2%, by weight, of the bis-AQA
surf~ t~nt~ in such compositions. Again, as in the case of the granular and liquid laundry
10 compositions, the weight ratio of the bis-AQA surfactant to other surfactants present in
such compositions is low, i.e., sub-stoichiometric in the case of anionics. Preferably, such
chP~nin~ compositions comprise bis-AQA/surfactant ratios as noted immP~ tPly above for
m~hinP-use laundry compositions.
15 In collLld~L with other cationic sulr~ known in the art, the bis-alkoxylated cationics
herein have s~rr~ l solubility that they can be used in combination with mixed surfactant
~y~ ,.,-s which are quite low in nonionic surf~ t~nt~ and which contain, for example, alkyl
sulfate surfaet~ntc. This can be an important consideration for fonm-l~tors of d~t~ L
compositions of the type which are conventionally designed for use in top loading
20 ~ o.-.~t;c washing m~hinP~, eSpeci~lly of the type used in North America, as well as
under J~ sc usage conditions. Typically, such compositions will cc~ lise an anionic
surfactant:nonionic ~u~r;~ l weight ratio in the range from about 25:1 to about î:25,
preferably about 20:1 to about 3:1. This can be co~ ds~d with Eul~ean-type forrnulas
which typically will co~ ,ise anionic:nonionic ratios in the range of about 10:1 to 1:10,
25 preferably about 5:1 to about 1:1.
The ~l~fel~cd ethoxylated c~tionie surf~rt~nt~ herein are available under the trade name
ET~OQUAD from Akzo Nobel Chpn~ Company. Allt;ll~ti~rely, such materials can be
~y~lhP~ d using a variety of dirrc,~ reaction schemes (wherein "EO" ~ ,e
30 -CH2CH2O- units), as follows.
- SCHEME 1
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16
RIOH + N H3 H2/Cat/Heat Rl N ~H
EXCESS H
R--N~ + 2 n~ BASECat~, Rl N--[(EO)nHl2
Rl N--[(Eo)nH]2 + CH3CI HEAT, Rl N+--[(EO)nH]2
CH3 cr
SCHEME 2
'N--[(Eo)2Hk + C H2 Cat ~ 3~N--[(EO) H]
CH
RIBr + N--r(EOkH]2 HEAT ~ Rl N+ [(EO)2H
CH3 Br
SCHEME 3
'N--[(EO)2Hk + C H2/Cat ~ 3~N--[(EO) H]
RlBr + N--[(EO)2Hl2 HEAT 1I Rl N--[(EO)2H]2
CH3 Br
15 SCHEME 4
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Cl--CH2CH2--OH + n~ ~ Cl--CH2CH20[EO~n--H
R--N~CH + 2 Cl--CH2CH20[EO]n--H HEAT~ Rl I _[CH2CH2O~EO~ 2
CH3 cr
An economical reaction scheme is as follows.
S SCH~ME 5
Rl 0~03~Na+ + H-N--[(EO)H32 HEAT ~ Rl N--r(EO)H32
Rl N--[(EO)Hk + 2 n~ HEAT ' Rl N--[(EO)(Eo)nE~2
Rl N--[(EO)(EOffl32 + CH3Cl ~ Rl I--~(EO)(EO~r~32
CH3 Cl
The following ll~Udlll.,t~ the optional and pl~,fe,led reaction con~litionc of
10 .SrhPmP 5. Step 1 of the reaction is preferably con~ ctP~l in an a~ueous ...e~ .. Reaction
Lt;lll~ d~ul~S are typically in the range of 14~-200~C. Reaction ~l~,s~ur~,s are 50-1000 psig.
A base catalyst, pl~r~,rably sodium hydroxide can be used. The mole ratio of ~ are
2:1 to 1:1 amine to alkyl sulfate. The l~,a~;lion is ~leLI~bly con~ rt~P(l using Cg-C14 alkyl
sulfate, sodium salt. The ethoxylation and yuaLeLl~i~Lion steps are carried out using
15 conventional con~ ?nc and re~rt~nt~.
Under some cil~ res reaction ~rhPmP 5 results in products which are sufficiently
soluble in the aqueous reaction mP~ m that gels may form. While the desired product can
be recovered from the gel, an alternate, two-step synthesis Sç~rmr 6, heleil~rt._~, may be
20 more desirable in some collllllcl-;ial ci~ .res. The first step in SchPmr 6 is con-l~-ct~Pd
as in Scheme 5. The second step (ethoxylation) is preferably con~iucted using ethylene
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oxide and an acid such as HCl which provides the ~~uaternary surfactant. As shown below,
chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl
derivative.
5 For reaction Scheme 6, the following parameters ~ .n~ the optional and ~ ed
reaction conditions for the first step. The first step is preferably co.~ in an aqueous
mf~Aillm Reaction Lenl~ Lul.,s are typically in the range of 100-230~C. R~ ar,tion
u,cs are 50-1000 psig. A base, preferably sodium hydroxide, can be used to reactwith the HSO4-gel,~,dled during the reaction, or an excess of the amine can be employed to
10 also react with the acid. The mole ratio of amine to aL~cyl 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
recovery step, the desired sub~LiLuLed amine is simply allowed to sc~at~: as a distinct
phase from the aqueous reaction mf~dillm in which it is insoluble. The second step of the
process is con~ ete~1 under conventional reaction conditions. Purther ethoxylation and
15 ~luak;lni~Lion to provide bis-AQA s~l~r~ are con~ ct-~1 under ~ a~ acLiou
conf1ition~.
S~h~m-~ 7 can optionally be conA~ te~;l using ethylene oxide under standard ethoxylation
conditions, but without catalyst, to achi~,~e monoethc)7tylation.
The following illu~ s these additional reaction scllPm~s, wherein "EO" Ic~ se~ the
-CH2CH2O- unit. In the reactions, ei~er an inorganic base, an organic base or excess
an~ine reactant is used to neutralize ge,l- ~t~ d HSO4.
25 S~h~me 6
H
R~OSO3 Nat + H,N--CH2CH2-OH ~ Rl N--CH2CH2-OH
IH ,CH2CH20H
R~ NCH2CH20H ~ ClCH2CH2~H ~ RIN~
CH2CH20H
~heIn~ 7
IH ~ ,CH2CH20H
R~N--CH2CH2OH No Catalyst 'EO~I
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The following further illustrates several of the above reactions solely for the
convenience of the formulator, but is not int~nfle~ to be limiting thereof.
Synthesis A
5 Pl~,araLion of N.N-Bis(2-hydroxyethYl)dodecylamine
J
To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles),
14.55 g of ~ th~nolamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution
(0.095 moles) and 72 g of ~i~t.ll.o(l 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 34
hours. The Ini~lUlG iS cooled to room l~ alule and the liquid contents of the glass liner
are poured into a 250 ml s~aLol~ funnel along with 80 ml of chloloÇui.,l. The funnel is
shaken well for a few ~ es and then the ~ Lllr~ is allowed to s~l,aldLe. The lower
chloloru,ll, layer is drained and the chlc,i..fo"" e~,h~ol~ted off to obtain product.
Syl,llle~is B
P~ alalion of N~N-Bis(2-hydroxyethvl)dode~;yl~h,e
1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of
base in the ~"al~l~l described in SyllLl,~sis A. The resll1tin~ 2-hydroxyethyldodecylamine is
l~co~,ered and reacted with l-chlolu~ ol to ~-e~a,~ the title co,~uulld.
SyllLllesis C
~alaLiull of N.N-Bis(2-l~vdruxy~;Lll~/l)dodecylamine
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 ~ till~cl ~2~- The glass liner is sealed into a 500 ml, st~inl~
steel, rocking ~uLoclave and heated to 160-180~C under 300400 psig nitrogen for 34
hours. The mixture is cooled to room le~ elalu~ and the liquid co~ of the glass liner
are poured into a 250 ml sepala~ul~ funnel along with 80 ml of chloroform. The furmel is
shaken well for a few ~ es and then allowed llPi~Lule to separate. The lower chloroform
layer is drained and the chlolorolll- is evaporated off to obtain product. The product is
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.
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The bis-substi~ted amines prepared in the foregoing Syntheses can be further ethoxylated
in standard fashion. Qu~ lion with an alkyl halide to fo~n ~e bis-AQA surf~ct~n
herein is routine.
S
According to the foleg()i~lg7 the following are nonlimitTn~, specific illustrations of bis-AQA
surf~rt~nt~ used herein. It is to be understood that the degree of alkoxylation noted herein
for the bis-AQA surf~rt~nts is reported as an average, following common practice for
conventional e~oxylated nonionic surfactants. This is because the ethoxylation reactions
10 typically yield mixtures of materials with differing deg~ees of ethoxylation. T~us, it is not
u~lco~ on to report total EO values other than as whole llu~lbc.~, e.g., "EO2.5~,
"EO3.5" .
Desi~nation Rl R2 ApR3 A~qR4
bis-AQA-1 C12-C14 CH3 EO EO
(also referred 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 E04)
bis-AQA4 Cl2 CH3 EO EO
bis-AQA-5 C12-C14 CH3 ~EO~2 (EO)3
bis-AQA~ C12-C14 CH3 ~EO~2 (EO)3
bis-AQA-7 Cg-C1g CH3 (EO)3 (EO)2
bis-AQA-8 C12-C14 CH3 (EO)4 (EO)4
bis-AQA-9 C12-C14 C2H5 (EO)3 (~O)3
bis-AQA-10 C12-C18 C3H7 (EO)3 (EO)4
3~
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bis-AQA-l 1 C12-C18 CH3 (propoxy) (EO)3
bis-AQA-12 Clo~C18 C2H5 (iso-propoxy)2 (EO)3
S bis-AQA-13 C1o~C18 CH3 ~EO/PO)2 (EO)3
bis-AQA-14 Cg-Clg CH3 ~E~~15* (E~)lS*
bis-AQA-lS Clo CH3 EO EO
bis-AQA-16 Cg-C12 CH3 EO EO
bis-AQA-17 Cg-Cl 1 CH3 ~ EO 3 .5 Avg. -
bis-AQA-18 C12 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 (E~)2
25 *Ethoxy, optionally end-capped witn methyl or ethyl.
Highly plefc.l~d bis-AQA compounds for use herein are of the formula;
Rl ~CH2CH20H
N X~
CH3/ ~CH2CH2OH
v~ Rl is Cg-C1g hydrocarbyl and ~ lul~S thereof, preferably Cg, Clo, C12, C14aL~cyl and mixtures thereof. X is any co..vel~ient anion to provide charge balance,
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22
preferably chloride. With reference to the general bis-AQA structure noted above, since in
a plerelled compound Rl is derived from coconut ~C12-C14 alkyl) fraction fatty acids, R~
is methyl and ApR3 and A'qR4 are each monoethoxy, this p-~fc~ d type of compound is
referred to herein as "CocoMeEO2" or "bis-AQA-1" in the above list.
S
Other bis-AQA surf~rt~nt~ useful herein include compounds of the formula:
R~ ~(CH2CH~O)pH
R2/ ~(cH2cH2o)q~
wherein R1 is Cg-C1g hydloc~byl, ~ Çel~bly Cg-C14 allyl, inf~pen~lently p iS 1 to 3 and
q is 1 to 3, R2 is Cl-C3 aLl~yl, preferably methyl, and X is an anion, especially chloride or
bromide.
Other compounds of the fol~goillg type include those wll~leill the ethoxy (CH2CH20) units
(EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2OI and ~CH2CH(CH30] units(i-Pr) or n-propoxy units (Pr), or Il~L~lUlC5 of EO and/or Pr and/or i-Pr units.
Non-AOA Detersive Surf~t~nt~
20 In addition to the bis-AQA ~ulr~e~l, the compositions of the present invention preferably
further CUl~ a non-AQA surfactant. Non-AQA surf~rt~nt~ may include ess~ti~1ly any
anionic, nonionic or additional cationic ~lr~clant.
~nionic Sulril~;lal.
Nonl;...i~;ng examples of anionic surf~rt~nt~ useful herein typically at levels from 1% to
55%, by weight, include the conventic)~l C11-C1g alkyl bel~ne sulfonates ('ILAS") and
primary ("AS"), branched-chain and random Clo-C20 aL~cyl sulfates, the C1o-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 + l) are inLegcls of at least 7, preferably
at least 9, and M is a water-solubilizing cation, especially sodium, ulLsaluldted sulfates such
as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the Clo-C18 sl-lf~t~l
polyglycosides, the C1o-C1g alkyl aLlcoxy sulfates ("AEXS"; especi~lly EO }-7 ethoxy
,
-
CA 02254818 1998-11-17
WO 971444~ PCT~US97/08373
23
sulfates), and the Clo-Clg alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates~. The C12-Clg betaines and sulfobetaines ("sultaines"), C1o-Clg
amine oxides, can also be inrl~ d in the overall compositions. Clo-C20 conventional
soaps may also be used. If high sudsing is desired, the branched-chain Clo-C16 soaps may
S be used. Other conventional useful surf~ct~ntc are listed in standard texts.
NoI~ionic Surfactants
Nonlimitin~ examples of nonionic sl~rf~ct~ntc useful herein typically at levels from 1% to
10 55%, by weight include the alkoxylated alcohols (AE's) and aLkyl phenols, polyhydroxy
fatty acid amides (PFAA's), aLkyl polyglycosides (APG's), Clo-Clg glycerol ethers.
More s~ccir,cally, the con~enc~ti-~n products of ~ nd~y and secondary aliphatic alcohols
with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonionic
15 ~.ulÇ~;L~lt in the present invention. The aLIcyl chain of the ~lirh~tir alcohol can either be
str~i~ht or blA"''I~r~1, p~ or secondaly, and generally contains from 8 to 22 carbon
atoms. I~cfcl,~d are the con~lenc~tion products of alcohols having an alkyl group
co..~ from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon atoms, with
from 1 tolO moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of
20 alcohol. Examples of co~ elcially available nonionic surf~rt~ntc of this type include:
TergitolTM 15-S-9 (the con~1enc~tion product of C11-C1s linear alcohol with 9 moles
ethylene oxide) and TergitolTM 24-L-6 NMW (the con-lenc~tion product of C12-C14
~~lin~l~ alcohol with 6 moles ethylene oxide with a narrow molecular weight di~ Lion),
both ~..~ d 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
con-len~ ;oll product of C12-C~ 3 linear alcohol with 3 moles of ethylene oxide),
NeodolTM 45-7 (the cont1~onc~tion product of C14-Cls linear alcohol with 7 moles of
ethylene oxide) and NeodolTM 45-5 (the con~i~onc~tion product of C14-Cls linear alcohol
with 5 moles of ethylene oxide) ..~.k~le~l by Shell ChPnnir~l Colll~.any; KyroTM EOB (the
30 co~..le~ ;on product of C13-Cls alcohol with 9 moles ethylene oxide), ~-~ c~l by The
Procter & Gamble Colllpally; and Genapol LA 030 or OSO (the con~ipn~tion produc~ of
- C12-C14 alcohol with 3 or 5 moles of ethylene oxide) .. ~.kelP~i by Hoechst. The ~icr~llcd
range of HLB in t'nese AE nonionic s~rf~rt~nt~ is from 8-11 and most pler~ d from 8-10.
Con-ien~tes with propylene oxide and ~utylene oxides may also be used.
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24
Another class of plefelled nonionic surfactants for use herein are the polyhydroxy fatty
acid amide surf~rt~ntc of the formula.
wll~.eill Rl is H, or Cl 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a llliX.lulC
thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydloc~l,yl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly conn~cte~ to the chain, or an
aL~coxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C11 ls aLkyl or
10 C1s 17 alkyl or aLkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived
from a reducing sugar such as glucose, fructose, m~ltose, lactose, in a reductive ~min~tion
reaction. Typical examples include the C12-Clg and C12-C14 N-methyl~l--c~mi-les. See
U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used;
see U.S. 5,489,393.
Also useful as the nonionic surfactant in the present invention are the allylpoly~acchalides
such as those disclosed in U.S. Patent 4,565,647, T.l~n~o, issued January 21, 1986,
having a hydrophobic group cont~ining from 6 to 30 carbon atoms, preferably from 10 to
16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group cont~ining
20 from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units.
Any ~.l.iri~ ,accha,ide cc-nt~inin~ 5 or 6 carbon atoms can be used, e.g., glucose,
g~l~rt ~se and galactosyl ~-.oi~:Ps can be s~b~ e~l for the glucosyl moieties (optionally
the hydrophobic group is ~tt~rh~d at the 2-, 3-, 4-, etc. position~ thus giving a glucose or
~l ~tose as opposed to a ~hlcosi/lP or ~ cto.cid~ The inter~acr}l~ride bonds can be, e.g.,
25 b~ ~n the one position of the additional saccl~ride units and the 2-, 3-, 4-, and/or 6-
positions on the l.lec~ s~ch~. .de units.
The l,.ef~ d aLkylpolyglycosides have the formula:
R20(CnH2nO)t(glycosyl~x
elGill R2 is s~ cte~l frorh the group consisting of alkyl, alkyl~h~l~yl, hydroxyaLkyl,
~ydlo~y~lkylphenyl, and ll~b~ul~s thereof in which the aLkyl groups contain from 10 to 18,
~ç~ bly from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10,
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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 prepare these compounds, the
alcohol or alkylpolyethoxy alcohol is formed first and t'nen reacted with glucose, or a
source of glucose, to form the glucoside (attacmnent at the 1-position). The additional
5 glycosyl units can tnen be qttq.-~h~l between their 1-position and the prece~lin~ glycosyl
units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
Polyethylene, polypropylene, and polybutylene oxide con~l~n~q-tes of aLkyl phenols are also
suitable for use as the nonionic surfactant of the surfactant ~y~llls of tne present invention,
10 with the polyethylene oxide con~ n.C~tes being ~le~.,~d. These con~ou.lds include the
conrlencqtion products of aLkyl phenols having an alkyl group co~ from 6 to 14
carbon atoms, ~l~r.,.a'oly from 8 to 14 carbon atoms, in either a straight-chain or
l~dnched-chain configuration with the alkylene oxide. In a ~lef~.-ed embo~iinl~nt~ the
ethylene oxide is present in an amount equal to from 2 to 25 moles, more ~l~f~dbly from 3
15 tolS moles, of ethylene oxide per mole of aL~cyl phenol. C~v.l~ ially available nonionic
su~ctqnt~ of this type include IgepalTM C0-630, Il~ c~d by the GAF G"poldlion; and
TritonTM X45, X-114, X-100 and X-102, all ma~ d by the Rohm & Haas Co-~a-ly.
These surfqct~nt~ are commonly reÇ~l.ed to as alkylphenol alkoxylates (e.g., alkyl phenol
ethoxylates).
The con~en~qtion products of ethylene oxide with a hydrophobic base formed by the
con~ q~i-,n of propylene oxide with propylene glycol are also suitable for use as the
qd~litinnq-l nonionic ~ulr~ in the present invention. The l~ydropl1obic portion of these
c~ ullds will preferably have a molecular weight of from 150Q to 1800 and will exhibit
25 water insolubility. The ~l(lition of polyoxyethylene moieties to this llydr~phobic portion
tends to ihl.;r,asc the water solubility of the molecule as a whole, and the liquid character of
the product is ~ Cd Up to the point where the polyo~ llylene content is 50% of the
total weight of the con-ien~qtion product, which corresponds to condensation with up to 40
moles of ethylene oxide. Examples of co~ .oul.ds of this type include certain of the
30 co..,.l.~..;ially-available PluronicTM surf~qrtqnt~ marketed by BASF.
- Also suitable for use as the nonionic surfactant of the nonionic ~.. r;.~ system of the
present invention, are the con-l~n~tion products of ethylene oxide with the product
r~snltin~ from the reaction of prowlene oxide and ethylen~ minP. The hydrophobic35 moiety of these products co.~i~ of ~e reaction product of ethylen~ minP and excess
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26
propylene oxide, and generally has a molecular weight of ~rom 2500 to 3000. Thishydrophobic moiety is Con~l~n~e(l with ethylene oxide to the extent that ~e condensation
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 surfactant include
S certain of the comm~rcially available TetronicTM compounds, marketed by BASF.
Additional Cationic surfactants
Suitable cationic surf~rt~nt~ are preferably water di~ ilJ}e compound having surfactant
10 pl~.Lcs COI~ g at least one ester (ie -COO-) linlcage and at least one cationically
charged group.
Other suitable cationic surf~rt~ntc include the q~ tl..U~y ammonium ~u,r~ ; select~d
from mono C6-C16, preferably C6-Clo N-alkyl or aL~cenyl ~ O~ surf~t~nt~ wlle..,.15 the rem~inin~ N positions are ~ub~ Led by methyl, hydroxyethyl or hydroxyl),u~yl
groups. Other suitable cationic ester surfactants, inrllldin~ choline ester ~u, r~ , have
for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
Qptional Detel~elll In~redients
The following illustrates various other optional ingredients which may be used in the
comrositinns of this invention, but is not int.on-lP~ to be limitin~ thereof.
Additional Bleach ~ent
The de~~ compositions herein may co~is~ an ~ tiorl~l bl~ in~ agent. Such
blP~ agents are typically present at levels of from 1 % to 20%, more typically from
3% to 15%, of the d~t~,.ge.lL composition, especi~lly for fabric laundering.
30 Other suitable blp~hin~ agents include chlorine and pholua~;livaLed blP~c~ agents.
Examples of photoactivated ble~-hin~ agents include the sulfonated zinc andfûr ~ mimlm
phthalo~;ya~ es. See U.S. Patent 4,033,718, issued July 5, 1977 to ~Iolcombe et al. If
used, det~ L compositions will typically contain from 0.025% to 1.25%, by weight, of
such bleaches, especially sulfonate zinc phthalocyanine.
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Bleach Activator
A plef~.r~d colu~ollelll of ~e composition of the present invention is a bleach a~;tivato~.
Bleach activators are typically present at levels of from 0.1% to 60 ~, more typically from
5 0.5% to 40% of the bl~rhing composition eu~ g the bleaf~ing agent-plus-bleach
activator.
Peroxygen ble~c~ agents, the perborates, etc., are preferably combined with bleach
activators, wnich lead to the in situ production in aqueous solution (i.e., during the
10 washing process) of the peroxy acid or peracid collcs~onding to the bleach activator.
Various nonl;.~ examples of activators are disclosed in U.S. Patent 4,915,854, issued
April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoylo~yl,e~ le
sulfonate (NOBS) and tetlaacelyl ~:~ylene rli~min~ (TAED) a~ tol~ are typica}, and
uub~lul~es thereof can also be used. See also U.S. 4,634,551 for other typical bl~oa~hP~ and
15 a~;livak~ls useful herein.
In an alh.,la~ e ~l~f~.red aspect a p1cfu.u,ed peracid is incorporated duc~Lly into the
composition. Co,n~osiliorls cont~inin~llli~lul~s of a hydlogcu peroxide source and bleach
a~ ,.ttor in combination with a preformed peracid are also envisaged
Highly ~l~rc.l~,d amido-derived bleach activators are those of the formulae:
RlN(R5)C(o)R2C(o)L or RlC(O)N(R5)R2C(o)L
~I1CLeih1 Rl is an alkyl group cont~ining from 6 to 12 carbon atoms, R2 is an aL~cylene
c~ ;.;n;~ from 1 to 6 carbon atoms, R5 is H or aLkyl, aryl, or aLkaryl C(J~ .;..g from 1
to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that
iS ~li~l~re~l from the bleach a~;liv~tol as a con~eqllerlre of the nucleophilic attack on tne
bleach a~;livator by tne pc.hydlolysis anion. A lllcr~led leaving group is phenyl sulfonate.
Preferred examples of bleach a~ tcns of the above formulae include (6-ocl;~n~--i(1o-
caproyl)oxyb~ n~.-lfonate, (6-nu--~n~ Qcaproyl)oxy~n~n~ lfonate, (6~c~..i~...i~io-
caproyl)o~yl,~ n~ lfonate, a~d mi~LLulcs thereof as described in U.S. Patent 4,634,551,
incorporated herein by refe~ ce.
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28
Another class of bleach activators co~ lises the benzoxazin-type activators disc~osed by
Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by
reference. A highly preferred activator of the benzoxazin-type is:
~N"C~
Still another class of pref~lred bleach activators includes the acyl lactam activators,
especially acyl caprolactams and acyl valerolactams of the fonmll~P:
O C--CH2--Ct~2
CH2--CH2
CH2--CH2
R6--C--N~
CH2--CH2
wll~ R6 is H or an aL~yl, aryl, a~coxyaryl, or alkaryl group co~ .n~ from 1 to 12
carbon atoms. Highly ~lefe.lcd lactam acliv~ol 7 include b~l~uyl caprolact~n, octanoyl
caprol~~t~rn, 375,5-L~ w~lylh~Y~nnyl caprolactam7 l~na"oyl caprol~ct~m, decanoylcaprolactatn, un-hoc~oTtoyl capro!~~,t~m, bel~uyl valerolactam, o~ yl valerolactatn,
decanoyl valerolactam, Im~lçc~nnyl valerolactam, nol~loyl valerolactam, 3,5,5-
LlinlcLllylh~ )yl valerol~t~m and n~L~lules thereof. See also U.S. Patent 4,545,784,
issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses
acyl caprol~t~m~, inrlll-lin~ benzoyl caprolactam, adsorbed into sodium perborate.
13uilders
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29
D~t~Lgcllt builders can optionally but preferably be included in the compositions herein, for
example to 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
variety of mPrll~nicm.c including forming soluble or insoluble complexes with har-ll,ess
5 ions, by ion exchange, and by offering a surface more favorable to the precipitation of
haldl~ss ions than are the surfaces of articles to be cleaned. Builder level can vary widely
depending upon end use and physical form of the composition. Built deLef~ typically
cc"l~lise at least 1% builder. Liquid form~ tionc typically co~ ise 5% to 50%, more
typically 5% to 35% of builder. Granular form~ ti~ns typically CO~ liSC from 10% to
80%, more typically 15% to 50% builder by weight of the del~.gelll cu~ o~ilion. Lower
or higher levels of builders are not exel~ pd For example, certain det,.gc.ll additive or
high-sulr~ form--l~tions can be lmhllilt
Suitable builders herein can be select~Pd from the group concictin~ of pho~lJh,.lrs and
15 polyphos~hdles, çcpeci~lly the sodium salts; silir~tPs inrlll~iit~ water-soluble and hydluus
solid types and inrlllrlin~ those having chain-, layer-, or three r~ on~ u~;LulC as
well as amorphous-solid or non-structured-liquid types; callJul~les, l~icall,olldt~s,
sesqllir-~rbonates and carbonate minerals other than sodium carbonate or sesquir-~ bo,h~te;
~Illmincsilir~tPs; organic mono-, di-, tri-, and tt;ll~eall,oxylates especially water-soluble
20 ~ l~ulr~ctant carboxylates in acid, sodium, pot~ccil~m or alkanolammonium salt form, as
well as oligomeric or water-soluble low molecular weight polymer e~lJo~ylates inr~ ing
~liph~tir and al~ ic types; and phytic acid. These may be compl~ f-A by borates,e.g., for pH-lJurf~,.mg purposes, or by sulfates, especi~lly sodium sulfate and any other
fillers or call;c~ which may be h~ l~L to the en~inpering of stable ~ulr~ andlor25 builder~ont~inin~ d~,~r~.ll coll,~o~ ;onc.
Builder ~l~lu~.,s, su...~;...Ps termed "builder ~y~l~ms" can be used and ~rpically comprise
two or more convention~l bllilfiPr~c~ optionally complf-..~ e~i by c~ ;, pH-buffers or
fillers, though these latter materials are generally accounted for separately when desclibi~g
30 qn~ntitiPs of materials herein. In terms of relative qll~ntitiPs of surfactant and builder in
the present det~,.g~ r~.~d builder systems are typically forml~l~t~P~ at a weight ratio
of surfactant to builder of from 60:1 to 1:80. Certain ~fe~l-ed laundry dt:l~.g~ 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
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P-cons~ining dete,gelll builders often ~ ,ed where permitt~-cl by legislation include, but
are not limited to, the alkali metal, ammonium and alkanolammonium salts of
polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric
meta-phosphates; and phosphonates.
Suitable silicate builders include alkali metal silirQtes, particularly those liquids and solids
having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1, including, particularly for automatic
dishwashing purposes, solid hydrous 2-ratio silicates Illalheled by PQ Corp. under the
tr~tlen~m~ BRITESIL0, e.g., BRITESIL H20; and layered ~ilir~tes, e.g., those described
10 in U.S. 4,664,839, May 12, 1987, ~I. P. Rieck. NaSKS-6, ~ $ abblt~,iate:d "SKS-
6", is a crystalline layered ~ ...-free ~-Na2SiOs morphology silicate ~ .k~lec~ by
Hoechst and is plcfelled especially in granular laundry compositions. See p~alive
mPth~lc in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such
as those having the general formula NaMSix02x + 1 ~yH20 wl~l~,m M is sodium or
hydrogen, x is a ~ lxr from 1.9 to 4, preferably 2, and y is a ~ lbcr from O to 20,
preferably 0, can also or ~lt~ tely be used herein. Layered silir~t~,s from Hoechst also
include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ~ and y layer-silicate forms. Other
silir~t~s may also be useful, such as m~ si..~- silicate, which can serve as a crispening
agent in granules, as a stabilising agent for bleaches, and as a component of suds control
systems.
Also suitable for use herein are synth~si7p(1 crystalline ion e~rrh~n~e materials or hydrates
thereof having chain structure and a composition ~ s~ d by t~e following generalformula in an anhydride form: xM20 ySiO2.zM'O wh~ M is Na and/or K, M' is Ca
and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711,
S~k~lr~ i et al, June 27,1995.
Suitable carbonate builders include ~Ik~lin~ earth and aLkali metal carbonates as disclosed
in German Patent App}ication No. 2,321,001 published on November 15,1973, ~Ithough
sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate
minerals such as trona or any convenient multiple salts of sodium carbonate and calcium
carbonate such as those having the composition 2Na2C03.CaC03 when anhydrous, andeven calcium carbonates including calcite, aragonite and vaterite, especially forms having
high surface areas relative to compact calcite may be useful, for example as seeds or for
use in synthetic del~lg~llL bars.
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31
minosilicate builders are Psreci~lly useful in granular del~e,lls" but can also be
incorporated in liquids, pastes or gels. Suitable for the present purposes are those having
empirical formula: [MZ(Alo2)z(sio2)v]-xH2o wherein z and v are hllegel~, of at least 6,
the molar ratio of z to v is in the range ~rom 1.0 to 0.5, and x is an integer from 15 to 264.
minosilir,~tes can be crystalline or amorphous, naturally-occurring or syn~hPtir~lly
derived. An ~ minosilicate production method is in U.S. 3,985,669, Krummel, et al,
October 12, 1976. P~efc.lcd synthetic crystalline ~II-minosilir~te ion e~rh~n~e materials
are available as Zeolite A, Zeolite P ~B), Zeolite X and, to whatever extent this differs
10 from Zeolite P, the so-called Zeolite MAP. Natural types, inrlntlin~ clinoptilolite, may be
used. Zeolite A has the formula: Nal2[(AlO2)12(SiO2~12]-xH2O WIIeLei1I X is from 20 to
30, especi~lly 27. Dehydrated zeolites (x = 0 - 10~ may also be used. ~r~ably, the
silicate has a particle size of 0.1-10 ~ ~, in ~ m~ter.
~-it~ organic d~,~c,.l builders include polycarboxylate compounds, including water-
soluble l~l~'ulr~ctant dicarboxylates and tricarboxylates. More typically builder
polycarboxylates have a plurality of carboxylate groups, preferabiy at least 3 carboxylates.
Carboxylate builders can be form~ t~1 in acid, partially neutral, neutral or o~ l,ased
form. When in salt form, alkali metals, such as sodium, pol~e;l--.., and lithinm, or
alkanola-l,llloluulll salts are preferred. Polycarboxylate builders include the ether
polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and
T ~m'nerti 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 inr~ ing cyclic and
alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydlo~y~olycarboxylates, copolymers of maleic
al,hydlide with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy bcl~elR-2, 4, 6-
tri~lllphonir acid; c~lJo~Ly~ lllylo~y~ cr;~;r acid; the various aLtcali metal, anl,l.ol.,ulll and
30 ~ ed ~UlllllOlliUlll salts of polyacetic acids such as ethylpnr~ r t~ reti~ acid and
nitrilotriacetic acid; as well as mrllitir acid, succinic acid, polymaleic acid, benzene 1,3,5-
tricarboxylic acid, carbu~yl-,clllyloxysuccinic acid, and soluble salts thereof.
~ Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g.,
for heavy duty liquid d~t~ ,e~l~" due to availability from renewable resources and
CA 02254818 1998-11-17
W O 97/44433 PCT~US97/08373
biodegradability. Citrates can also be used in granular compositions, especially in
conlbillation with zeolite and/or layered silic~te~. Oxydisu;ci~les are also especially
useful in such compositions and col,lbh~lions.
Where permitted, and especially in the formulation of bars used for hand-laundering
operations, alkali metal phosphates such as sodium tripolypho~haL~s, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as
ethane-l-hydroxy-1,1-dipho~holLate and other lcnown 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 ~nti~c~in~ ~lo~ ies.
Certain det .s.ive surf~ t~nt~ or their short-chain homologs also have a builder action. For
unambiguous formula accuu~ g purposes, when they have ~.ulr~;lan~ capability, these
materials are snmm~ up as deLe.~.ive s~l~racLa~ cfi,.lcd types for builder functionality
15 are illustrated by: 3,3-dicarboxy4-oxa-1,6-h~ e~lio~tl?s and the related compounds
disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the
Cs-C20 aL~cyl and aLIcenyl succinic acids and salts thereof. S~lrcin~te builders also include:
laurylsuccinate, myristyl~l~rcin~tP~ palmityl~.,eei..~l~, 2-dodecenyh.ucc;il~dLe (~.eÇe.l~,d), 2-
pr~t~tlecenylsuccinate. Lauryl-succi,~l~s are described in Eulo~dll Patent Application
86200690.5/0,200,263, published Novem'oer 5, 1986. Fatty acids, e.g., C12-Clg
monocarboxylic acids, can also be incvlL~u~led into tne compositions as sulr~L~llL/builder
materials alone or in combination with the aÇol~ ned builders, especially citrate
and/or the succinate builders, to provide ~rlhion~l builder activity. Other suitable
polycarboxylates are disclosed in U.S. 4,144,226, C~lt~t fiPld et al, March 13, 1979 and in
U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.
Other types of ilh,.ganic builder materials which can be used have tne for~ula (MX)i Cay
(CO3)z wh~ l x and i are i~ e~ from 1 to lS, 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 s~ti~fir~1 such that the
formula has a neutral or "b~l~nre(l" charge. These builders are re~erred to herein as
"Mineral Builders". Waters of hydration or anions other than carbonate may be added
provided that the overall charge is b~1~nred or neutral. The charge or valence effects of
such anions should be added to the right side of the above equ~ti~ n Preferably, there is
35 present a water-soluble cation selected from the group collsi.~ of hydrogen, water-
CA 02254818 1998-11-17
WO 97J44433 PCTnUS97~83~3
33
soluble metals, hydrogen, boron, ammonium, silicon, and ~ LLules thereof, more
preferably, sodium, potassium, hydrogen, lithillm, ammonium and ~ Lules thereof,sodium and potassium being highly preferred. Nonlimiting examples of nolle~,1,onate
anions include those sel~cte~l from the group col~7i~ g of chloride, sulfate, fluoride,
5 oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mi~Lules thereof.
~f~..ed builders of this type in their simplest forms are selected from the group
consisting of Na2Ca(CO3)2, K2Ca(CO3)2, Na2Ca2(CO3)3, NaKCa(CO3)2,
NaKCa2(CO3)3, K2Ca2(CO3)3, and combinations thereof. Anespecially pr~r~ d
material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline
10 mo~ific~tions. Suitable builders of the above-defined type are further illustrated by, and
inrll- te, the natural or synthetic forms of any one or colllbh,ations of the following
minerals: Argha~ , Andersonite, Ash~;,orLi~leY, Beyerite, Borcarite, Bulb~i~
Rlltschliitt~, Cal~lillilc, Carbocernaite, Calletonile, Davyne, DOI~layi~t:Y, Fairchildite,
7Ulilc, I~ J~ er oyi~, Gaylussilc, Girvasite, C1egol~/i~, Jouravskite,
15 K~ )h~?jleY~ KCIL11~ lC~ Kh~nn~shite, Lc~..,ullllilcGd, Liottite, MckelveyiteY,
Microsornmite, Mroseite, NaLl~,r~ ite, N~ .c.~ , Rclnolldil~Ce, Sacrorallilc,
Schrocl~ingc.ilc, Shortite, Surite, Tunisite, T ~c~nit~, Tyrolite, Vishnevite, and Zemkorite.
E~cr~ ,d mineral forms include N~.,re.il~, Fairchildite and Shortite.
20 l~nzymes
El.~yllles can be included in the present dt;lclgcn~ colllposilions for a variety of purposes,
inrl~ in~ removal of protein-based, carbohydrate-based, or Lliglycclide-based stains from
~ul)~Lldt~,s, for the prevention of refugee dye Llal~r.,. in fabric laundering, and for fabric
25 lc~loldLion. Suitable cl~yllles include ~ lcascs, amylases, lipases, cell-~t~es, peroxidases,
and l~ urus thereof of any suitable origin, such as vegetable, animal, bacte.iaL fungal and
yeast origin. I~f~,~lcd se~ction~ are i~ ed by factors such as pH-activity and/or
stability optima, thPrmost~hility, and stability to active deLe ,.lL~, builders. In this respect
bacterial or fungal el~ylllcs are pl~,Çcll~,d, such as bactc-ial amylases and p~oL~ascs, and
30 fungal cellnl~çs.
~ "Detc,~ivc enzyme", as used herein, means any enzyme having a c~nin~, stain removing
or other~,vise ~neficial effect in a laundry, hard surface cle~ g or ~e.sollal care dcte~ L
composition. Prercll~d detersive enzymes are hydrolases such as plOt ases, amylases and
3~ lipases. ~cr~lcd enzymes for l~ul~ly purposes include, but are not limited to, proteases,
CA 02254818 1998-11-17
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34
cellulases, lipases and peroxidases. Highly preferred for automatic dishwa~lli~ are
amy1ases and/or proteases.
Enzymes are normally incorporated into d~ clll or d~le,~ellt additive compositions at
5 levels sufficient to provide a "cL ~nin~-effective amount". The term "cle~nin~ effective
~monnt" refers to any amount capable of producing a cle~ning, stain removal, soil removal,
whhenin~, deodorizing, or freshness improving effect on sub~llales such as fabrics,
disl,~are. In practical terms for current colln,lf r~ial pl~alions, typical amounts are up
to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the
10 detc~gen~ cu~ o~ilio.,. Stated otherwise, the compositions herein will typically col"~lise
from 0.001 % to 5 %, preferably 0.01 %-1 % by weight of a co~mnf ~-;ial C~ylllC
yle~dlion. Protease el~yllles are usually present in such collll"el-;ial ~le~a~aLions at
levels ~rriri~ to provide from 0.005 to 0.1 Anson units (AU) of activity per grarn of
composition. ~or certain d~t~ nL~, such as in 5..110~ ' dishwashing, it may be desirable
15 to increase the active ~l~ylnc content of the Cull~l~lf l~ial ~ret>alalion in order to Illillill~i~e
the total ~mollnt of non-catalytically active materials and thereby improve spuLLing/filming
or other end-results. Higher active levels may also be desirable in highly conce--Lldted
~ formulations.
20 Suita~le examples of proteases are the subtilisins which are obtained from particular strains
of B. subtilis and B. Iich~,.iJ~rrr.is One suitable protease is obtained from a strain of
~a~ , having ...-xi...--... activity throughout the pH range of 8-12, developed and sold as
ESPERASE0byNovoT~ rsA/SofD~ - k he~ art~l "Novo". The~ alalionof
this t;l~yll~ and analogous C~,~ S iS described in GB 1,243,784 to Novû. Other suitable
25 ~lut~,ases include ALCALASE~ and SAVINASE~9 from Novo and MAXATASE0 from
T.,t.c,.~ional Bio-Sy-~ s, Inc., The Netherlands; as well as Protease A as ~ close~l in
EP 130,756 A, January 9, 1985 and E~ut~,ase B as disclosed in EP 303,761 A, April 28,
1987 and EP 130,756 A, January 9, 1985. See also a high pH ~rotease from Bacillus sp.
NCIMB 40338 described in WO 9318140 A to Novo. El~ylllalic del~Lge~ comprising
30 protease, one or more other el~yl~les, and a reversible ll~otease inhibitor are described in
WO 9203529 A to Novo. Other pl~Ç~ d proteases include those of WO 9510591 A to
Procter & Garnble . When desired, a protease having decreased adsorption arld increased
hydrolysis is available as described in WO 9507791 to Procter & Galnble. A ,econ~bi~
trypsin-like protease for del~ ,ell~ suitable herein is described in WO 9425583 to Novo.
,
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W~ 97~44433 P~TAUS97/08373
In more detail, an especially ~rcre.led protease, referred to as "Protease 1:)" is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is derived
from a precursor carbonyl hydrolase by substihlfing a dirrclcllL amino acid for a plurality of
amino acid residues at a position in said carbonyl hydrolase e~uivalent to position +76,
5 preferably also in combination with one or more amino acid residue positions equivalent to
those selected from the group co~ of +99, +101, +103, ~104, +107, ~123,
+27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +2~4, +206,
+210, +216, +217, +218, +222, +260, +265, and/or +274 according to the
llUlnl)elillg of R,7ci~ anyloliql~fnci~ns subtilisin, as described in the patent applications
10 of A. Baeck, et al, entitled "Plot,_ase-Co~ h-~ Cleaning Colll~osilions" having US Serial
No. 08/322,676, and C. Ghosh, et al, "B~ rhin~ Compositions Colllp~ Protease
Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994.
Amylases suitable herein, especially for, but not limited to a~ ic dishwashing
purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;
RAPIDASE~, T..t~ l jon~l Bio-Synthr~ti~s, Inc. and TERMAMYL~, Novo.
FUNGAMYL'D from Novo is especi~lly useful. F.~ tlhlg of Cl.~yllRS for improved
stability, e.g., oxidative stability, is known. See, for e,~a,l,~lc J. Biological Chem., Vol.
260, No. 11, June 1985, pp. 6518-6521. Certain ~lerel~ed embo~ of the present
20 compositions can make use of amylases having improved stability in dct~r~cllL, such as
~--tom~tic dishwashing types, especially improved oxidative stability as lllea~ul~d against a
,~Ç.,rc.lce-point of TERMAMYL~ in coll~.cial use in 1993. These ~ rc~led amylases
herein share the cl~ of being "stability e.~h~ ecl " amylases, ch~,~ , at a
n~ .-, by a measurable ~ )love.l~llL in one or more of: oxidative stability, e.g., to
25 hydrogen peroxide/l~ lylelllyl-~nP-liA..~i..f in burf~l~d solution at pH 9-10; thPrrn~l
stability, e.g., at CO111ILOn wash ~e~ ...cs such as 60~C; or ~Ik~linr stability, e.g., at a
pH from 8 to 11, lu~a ,~.,d versus the above-i-lentifiP~I lef~ nce-point amylase. Stability
can be measured using any of the art-disclosed technir~l tests. See, for example, r~lel,ces
rlicclosecl in WO 9402597. Stability~l~h~n~e~l amylases can be obtained from Novo or from
30 (~el.f l~ or Il,le"la~iorlal. One class of highly preferred all~lases herein have the
co~ ol~ality of being derived using site-directed mutagenesis from one or more of the
R~ alllylases, especially the R~7cil~ a-a nylases, regardless of whether one, t~,vo or
multiple ~llylase strains are the immf ~ te precursors. Oxidative stability~ h~red
~ amylases vs. the above-i(lc-.~;r.rd leÇ~ ce amylase are plc:r~,llcd for use, especially in
35 ble~rhing, more preferably oxygen bleaching, as distinct from chlorine ble~ehi~
CA 02254818 1998-11-17
W O 97/44433 PCT~US97/08373
36
deL~.gellL compositions herein. Such plerell~d amylases include (a) an amylase according to
the h~Lei~l~er ~l~ incorporated WO 9402597, Novo, Feb. 3, 1994, as ~urther illustrated by a
mutant in which substitution is made, using alanine or threonine, preferably threonine, of
the methionine residue located in position 197 of the B lichenifonnis alpha-amylase, known
S as TERMAMYL~, or the homologous position variation of a similar parent amylase, such
as B. anyloliquefaciens, B. subtilis, or B. stearothermophilus; ~o) stability-enh~nrec~
amylases as described by (~e~ ror IllL.,~-Ialional in a paper entitled "Oxidatively Resistant
alpha-Amylases" ~.escl,led at the 207th American Ch~omir~l Society National l~eetin~,
March 13-17 1994, by C. Mitrhin~on. Therein it was noted that bleaches in ~ ;r
10 dishwashing dc~l~ellLs h~;liv~Lt: alpha-amylases but that improved oxidative stability
amylases have been made by Gell~llco~ from B. Iicheniformis NCIB8061. MeLllio~ e(Met) was i :lerltifird as the most likely residue to be mor~ ed Met was ~ub~ilu~d, one at
a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific .. ~
particularly irnportant being M197L and M197T with the M197T variant being the most
stable e~lessed variant. Stability was llleas.~ied in CASCADE~ and SUNLIGHT~; (c)
particularly pl~r~:lrtd amylases herein include amylase ~a.ial.L~ havin~ additional
m~ifir~tion iII the j,~".~ parent as described in WO 9510603 A and are availablefrom the ~csi~n~e, Novo, as DURAMYL~. Other particularly ~l~f~ d oxidative stability
ç-.1~.red amylase include those de3-;lil~d in WO 9418314 to (~ rQlIllL~ o~ and
WO 9402597 to Novo. AIIY o~er oxidative stability e--h~l-red amylase can be used, for
example as derived by site-directed mutagenesis from known chimeric, hybrid or simple
mutant parent forms of available amylases. Other l,lef~ ,d el~ylllc modific~tions are
aecç~sible. See WO 9509909 A to Novo.
Other amylase e l~yllles include those ~lPscrihe~l in WO 95/26397 and in co-p~nd.llg
application by Novo Nordisk PCT/DK96/00056. Specific amylase el~yllles for use in the
dct.,r~,c.ll compositi-)n~ of the present hlvelllion include a-amylases characterized by having
a s~ec;lir activity at least 25% higher than the ~ecir~c activity of Te.malllyl~ at a
~nl~c~àlulc range of 25~C to 55~C and at a pH value in the range of 8 to 10, lllea~ulcd by
the Ph~'lPb~ a-a~llylase activity assay. (Such Ph~deb:~c~9 oc-amylase activity assay is
dcs~ilil)cd at pages 9-10, WO 95/26397.) Also included herein are a-amylases which are at
least 80% homologous wi~ the amino acid sequences shown in ~e SEQ ID listings in the
~Çcl._.lces. These el~yll~es are ~lerelably incorporated into laundry deLcl~llL
compositions at a level from 0.00018% to 0.060% pure el~yllle by weight of the total
CA 02254818 1998-11-17
WO g7/44433 P ~ nUS97~8373
37
composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the
total composition.
Ce~ es usable herein include both bacterial and fungal types, preferably having a pH
S opLil,lulll between S and 9.5. U.S. 4,435,307, lBarbesgoard et al, March 6, 1984,
discloses suitable fungal cell~ es from Humicola insolens or Humicola strain DSM1800
or a c~ e 212-producing fungus belonging to the genus Aeromonas, and cellulase
extracted from the llel,alopall ;leas of a marine m~ , Dolabella Auricula Solander.
Suitable cell~ ees are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
10 2.247.832. CAREZYME~' and CELLUZYMEa9 (Novo) are esp&ci~l1y useful. See also
WO 9117243 to Novo.
Suitable lipase enzymes for d-,t~ usage include those produced by microo,~ .n~ of
the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as ~ closecl in GB
15 1,372,034. See also lipases in J~p~nlose Patent Application 53,20487, laid open Feb. 24,
1978. This lipase is available from Amano Ph~ A('~ i('A~ Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," or "Amano-P." Other suitable commercial
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 viscosum lipases from U.S. Bioc~ AI Corp., U.S.A. and Disoynth Co.,
The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~ enzyme derived
from Humicola lanuginosa and c~.n...~rcially available from Novo, see also EP 341,947,
is a pler~ d lipase for use herein. Lipase and amylase valiall~ stabilized against
peroxidase el~yl-les are ~iPs~. ihe~l in WO 9414951 A to Novo. See also WO 9205249 and
RD 94359044.
In spite of the large l~ullllxl of publications on lipase el~yllRs, only the lipase derived from
Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found
-widespread application as additive for fabric washing products. It is available from Novo
Nordisk under the tr~den~m~ Lipolasen', as noted above. In order to c~ e the stain
removal p~.ro.l,lallce of Lipolase, Novo Nordisk have made a llulll~l of valiall~. As
described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase
illllJll~Vt S the lard stain removal efficiency by a factor 4.4 over the wild-type lipase
r ~ ~ynRSCOlll~al~d in an amount lallgillg from 0.075 to 2.5 mg protein per liter).
Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses
CA 02254818 1998-11-17
W O 97/44433 PCTrUS97/08373
38
that the lipase variant (D96L) may be added in an amount co.re~onding to 0.û01-lû0- mg
(5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides
the bellefit of improved whi~ s m~ r~ re on fabrics using low levels of D96L variant
in deLergellL compositions cont~ining the bis-AQA surf~ct~nts in the manner disclosed
S herein, especially when the D96L is used at levels in the range of 50 LU to 8500 LU per
liter of wash solution.
Cl~tin~e enzymes suitable for use herein are described in WO 8809367 A to Ce n~ or.
10 Peroxidase enzymes may be used in combination with oxygen sources, e.g., ~l- ~l,onate,
perborate, hydrogen peroxide, etc., for "so}ution bl~ehing" or prevention of tla~r~ of
dyes or pigmlont~ removed from ~ub~Llales during the wash to other subsL,~t,s present in
the wash solution. Known peroxidases include horseradish pelo~idase, li~nin~e, and
haloperoxi~ es such as chloro- or bromo-peroxidase. Peroxidase-c~?.3~ g d~lge~
15 co~ o~ilions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.
A range of el~yllle materials and means for their illCO~ dLiOn into ~y~ ic detel~e~l
compositions is also disclosed in WO 9307263 A and WO 9307260 A to ('e ~nrQl
20 T~ ional, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty
et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in
U.S. 4,507,219, Hn~hPs, March 26, 1985. Enzyme materials useful for liquid d~ gc;nL
forTmll~tir~n~, and their incc,l~olalion into such form~ tinn~, are ~ rlose(i in U.S.
4,261,868, Hora et al, April 14, 1981. Enzymes for use in d~tel~ can be stabilised by
25 various teehniq~es. l:~l~ylllc stabi~ tion techniques are disclosed and e,~ llplirled in U.S.
3,6û0,319, August 17, 1971, Gedge et al, EP 199,405 and EP 2Q0,586, October 29, 1986,
Venegas. l~yllle st~bili~ti~n ~y~ s are also described, for e~ le, in U.S.
3,519,570 A usefill R~rilll-~, sp. AC13 giving p.ol~ases, xylanases and c~ os, is
desclil)cd in WO 9401532 A to Novo.
Enzyme Stabilizin~ System
The enzyme-cont~inin~ CWll~)OSiliOrlS herein may optionally also coll~lise from 0.001 % to
10%, preferably from 0.01)5% to 8%, most preferably from 0.01 % to 6%, by weight of an
35 ~ Gylllc stabilizing system. The enzyme stabilizing system can be any stabilizing system
CA 02254818 1998-11-17
WO 97/444~3 PCT~US97/08373
39
which is compatible with ehe detersive enzyme. Such a system may be inherently provided
by other formulation actives, or be added separately, e.g., by the form~ tQr or by a -
m~n-lf~t lrer of delcl~scn~-ready enzymes. Such seabilizing ~ Lellls can, for example,
r comprise calcium ion, boric acid, propylene glycol, shore chain carboxylic acids, boronic
acids, and mixtures ehereof, and are designed to address dirre~nL stabilization problems
~lepe~ inE on the type and physical form of the dclef~ l composition.
One stabilizing aL~loacll is the use of water-soluble sources of c~ m and/or m~ s;n.-~
ions in the ~mi~hP(~ c~ o~ilions which provide such ions to the enzymes. Calcium ions
are generally more errc~ e ehan m~ Ps~ ions and are ~lcfelled herein if only one type
of cation is being used. Typical dct~ ll compositions, especially liquids, will COmpliSe
from about 1 to about 30, preferably from about 2 eo about 20, more preferably from about
8 to about 12 millim~les of c~lci--m ion per liter of fini~hPd dclcl~clll co~ o~i~ioll, though
variation is possible d~endill~ on factors including the multiplicity, eype and levels of
el~y.~les inco.~ordL~ d. Preferably water-soluble calcium or m~ salts are employed,
inrln~lin~ for example c~lrinm chloride, calrillm hydroxide, calcium formate, calcium
malate, calcium m~lP~tP, calcium hydroxide and calcium aceeate; more generally, calcium
sulfate or m~y--~s;--.n sales coll~ol~ding to the exemplified calcium salts may be used.
Further i..c:l~,ased levels of C~lrinm and/or ~ P~vl~l may of course be useful, for
20 example for ~ the grease-cutting action of certain types of surfactant.
Another stabilizing a~l~ach is by use of borate species. See Severson, U.S. 4,537,706.
Borate stabilizers, when used, may be at levels of up to 10% or more of the cornposition
though more typically, levels of up to about 3% by weight of boric acid or other borate
25 cou-~oullds such as borax or orthoborate are suitable for liquid del~.~g.,.lL use. S~ss~ P~
boric acids such as phenylboronic acid, buLal~cbolol~ic acid, p-bromophenylboronic acid or
the like can be used in place of boric acid and reduced levels of total boron in de~lg~
compositions may be possible though the use of such sllbstitllt~ boron dc.iva~ s.
30 Stabilizing ~y~ ls of certain cl~ Y col~l~osilions, for example ~Illo~ lir dishwashing
~ compositionc, may further co~ ;se from 0 to 10%, preferably from 0.01% to 6~ by
weight, of chlorine bleach sca~ cr~, added to prevent chlorine bleach species present in
many water supplies from ~ rL il~ and inactivating the enzymes, especially under ~lk~lin~o
- conditions. While chlorine levels in water may be small, typically in the range from 0.5
35 ppm to 1.7~ ppm, the available chlorine in the total volume of water that comes in contact
CA 02254818 1998-11-17
W 097/44433 PCT~US97/08373
with the enzyme, for example during dish- or fabric-washing, can be relatively large;
accordingly, enzyme stability to chlorine in-use is som~tim~s problematic. Sincepercarbonate has the ability- to react with chlorine bleach the use of additional stabilizers
against chlorine, may, most generally, not be essel";~l, though improved results may be
S obtainable from their use. Suitable chlorine scavenger anions are widely known and
readily available, and, if used, can be salts C(J~ t;~ g ammonium cations with sulfite,
bisulfite, thiosulfite, ~hioslllf~te, iodide, etc. Antioxidants such as ca~ ate, ascolbal~,
etc., organic amines such as ethylenPdi~ lrt~dcetic acid (EDTA) or aL~cali metal salt
thereof, monoethanolamine (MEA), and ~ ur~s thereof can likewise be used. Likewise,
10 special enzyme inhibition ~.y~tellls can be i~lcol~tulaled such that dirf~,.e,ll ~"~ynles have
m~ximllm compatibility. Other conventional scavengers such as bisulfate, nitrate, ch}oride,
suuices of hydrogen peroxide such as sodium perborate tetrahydrate, sodium ~ll,oldle
monohydrate and sodium ~~r~;al~.olldle, as well as phosph~te~ co.~ phosphate,
acetate, benzoate, citrate, ~Illlale, lactate, malate, tartrate, salicylate, etc., and llPixlu~s
15 thereof can be used if desired. In general, since the chlorine scavenger rull~lion can be
~lÇ~Illled by hlgledi~ separately listed under better recognized functions, (e.g.,
llydr~,gcn peroxide sources), there is no absolute re-luh~ to add a separate chlorine
scavenger unless a co~ vulld ~.~lrul~ g that function to the desired extent is absent from
an cl~ylllc cc..~ .ing embodiment of the invention; even then, the scavenger is added only
20 for ~illluul results. Moreover, the forml-l~tor will exercise a rh~ t's normal skill in
avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as
fonmll~tPd, with other lea -live hlg.e.iic~ .. In relation to the use of ammonium salts, such
salts can be simply admixed with the deleLgelll composition but are prone to adsorb water
and/or liberate ammonia during storage. Accordingly, such materials, if present, are
desirably pl.jt~Ltd in a ~alliclc such as that desc~il~d in US 4,652,392, R~gin~l i et al.
Polvmeric Soil Release A~ent
Known polymeric soil release agents, hereinafter ''SRA'I or "SRA's", can optionally be
30 employed in the present detcrgell~ compositions. If lltili7~ , SRA's will generally comprise
from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by
weight, of the composition.
Pl~f~.led Sl~A's typically have hydrophilic segments to hydrophilize the surface of
3~ hydrophobic fibers such as polyester and nylon, ~nd hydrophobic se~n~nt~ to deposit upon
CA 02254818 1998-11-17
W O 97~44433 PCT~US97~8373
hydrophobic fibers and remain adhered thereto through co~ letion of washing and rinsing
cycles thereby serving as an anchor for the hydrophilic se~",cml~,. This can enable stains
oc-;ùlring ~,ul>se~ucu~L to Ll~,dll~lclll with SRA to be more easily cleaned in later washing
procedures.
s
SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S.4,956,447), as well as nr n~k~.~ed mollc.n~l units and structures may be linear, br~nrh~d
or even star-shaped. They may include cdl?~h~g moieties which are e~cpeci~lly effective in
controlling molecular weight or altering the physical or surface-active l,rop.,.lies.
lQ Structures and charge distributions may be tailored for application to dirr~r~ fiber or
textile types and for varied dct~ cll~ or d~ nl additive products.
fe,led SR~'s include oligomeric teleph~ te esters, typically ~l~alcd by ~lucesses
involving at least one l~ est~ .ir,calion/oligo~ alion, often with a metal catalyst such as
15 a l;~ ..aV) aL~coxide. Such esters may be made using a~ hi-n~l monomers capable of
being illcc,l~olàted into the ester structure through one, two, three, four or more positions,
without of course fol""~l a densely crosslinked overall structure.
Suitable SRA's include: a sulfonated product of a ~ ly linear ester oli~o,l~.,.
20 co~ lised of an oligo"" ~ic ester backbone of terephthaloyl and oxyalkyleneoxy repeat
units and allyl-derived sulfonated ~.,..;,,~1 moieties covalently ~ cl to the backbone, for
example as described in U.S. 4,968,451, No~.lll)er 6, 1990 to J.J. Scheibel and E.P.
Gosselink such ester oligonle.s can be ~r~ed by (a) ~l,o~Lylalillg allyl alcohol, (b)
l~acL~g the product of (a) with dinl.,~llyl t~ Jh~ te ("DMT") and 1,2-propylene glycol
("PG") in a two-stage Ll~ ei,t~,-irlcdlion/ oligoll.,.i,alion ploce lul~; and (c) I~.a~;lul~ the
product of (b) with sodium metabisulfite in water; the nonionir end~apped 1,2-
propylene/polyoxy~ ylene t~ te polyesters of U.S. 4,711,730, Dect;,l,~. 8, 1987
to Gosselink et al, for example those produced by ~ .se~.iri~,alion/oligo~ on ofpoly(ethylel~lycol) methyl ether, DMT, PG and poly(ethylel~e~ly-;ol) ("PEG"); the partly-
and fully- anionic-end-capped oligo~ .ic esters of U.S. 4,721,580, January 26, 1988 to
Gos.~elin~, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-
l,ydro~yoct~n~snlfonate; the nonionic-capped block polyester oligomeric colllpoLllds of
U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, Me-
~ capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped
PEG and Na-dimethyl-5-sulfois~l.~t.~l~te; and the anionic, especially sulfOal~yl, end-
CA 02254818 1998-11-17
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42
capped terephth~l~tp 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 conditioI~ing
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 terephth~ te or propylene
L~ te with polyethylene oxide or polypropylene oxide le~c~h~ te~ see U.S.
3,959,230 to Hays, May 25, 1976 and IJ.S. 3,893,929 to R~ r, July 8, 1975; cellulosic
10 dc,;v~livcs such as the hydroxyether cellulosic polymers available as METHOCEL from
Dow; and the Cl-C4 aIkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093,
Decçmhçr 28, 1976 to Nicol, et al. Suitable SRA's characterised by poly(vinyl ester)
llydl~hobe segments include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl
esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide bachl,~,l~s. See
15 Eul~eall Patent Applif ~tio~ 0 219 048, published April 22, 1987 by Kud, et al.
Coll~llercially available e~z....l,les include SOKALAN SRA's such as SOKALAN HP-22,
available from BASF, Gclll~ly. Other SRA's are polyesters with repeat units cont~inin~
10-15 % by weight of ethylene terephth~l~te together with 90-80% by weight of
polyoxyethylene l~c~ AI~te, derived from a polyoxyethylene glycol of average molecular
weight 300-5,000. Colll,llcl~;ial examples include ZELCON 5126 from Dupont and
MILEASE T from ICI.
Another preferred SRA is an oligomer having empirical formula
(CAP)2(EG/PG)s(T)s(SIP)1 which colll~-ises ~r~ph~llaloyl (T), sulfoisophthaloyl (SIP),
oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is l)le~.~bly l.~
with end-caps (CAP), ~,~f~,l~ly mc~ifi-od isethionates, as in an oligomer co,~ ing one
sulfoisophthaloyl unit, S te.ephlllaloyl units, o~yt:Lhyleneoxy and oxy-1,2-~o~ylelRo~y
units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units
derived from sodium 2-(2-hydroxyethoxy)-eth~nPs~llfonate. Said SRA preferably further
coll,~iises from 0.59~ to 20~, by weight of the oligomer, of a cryst~llinity-reducing
stabiliser, for example an anionic surfactant such as linear sodium dodecylb~ P~ 1fonate
or a m~rnhP~r selpcte~l from xylene-, cllmPn~-~ and toluene- sulrol~tes or ~ u~es thereof,
these stabilizers or modifiers being introduced into the ~y"lllesis pot, all as taught in U.S.
5,415,807, Gossçlink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for
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43
the above SRA include Na 2-(2-hydroxyethoxy)-eth~n~sl-lfonate, DMT, Na- dimethyl 5-
sulfoisophth~ , EG and PG.
Yet another group of ~-cÇ~ ed SRA's are oligomeric esters comprising: (1) a backbone
co~ li.7hl~ (a) at least one unit selected from the group co~ of dihydroxysulfonates,
polyhydroxy sulfOllalcs, a unit which is at least Llirunc;lional whereby ester lirtr~ges are
formed resulting in a blallclled oligomer backbone, and combinations thereof; (b) at least
one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a
1,2-oxyaLlcyleneoxy moiety; and (2) one or more ca~ lg units se!ecte~l from nonionic
10 ca~ g units, anionic capping units such as alkoxylated, preferably ethoxylated,
isethionates, alkoxylated ~lOp~ rOl~dlcs, aL~oxylated l)lo~a..~ lfonates, aLkoxylated
phenolsulfonates, sulfoaroyl derivatives and ll~i~lureS t'nereof. ~c;fe.l~,d of such esters are
those of ~ ical formula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y" '(T)z(SIP)z'(SEG)q(B)m}
wLI,lcil~ CAP, I~G/PG, PEG, T and SIP are as defined he~ al)ovc, (OEG) r~Les~
di(oxyethylene)o~y units; (SEG) l~les~,llLs units derived from the sulfoethyl ether of
glyce~ and related moiety units; (B) l~l.,se.ll~ bl~ units which are at least
l~irL~ ;Liol~l wlRl~by ester link~gec are formed resl~ltir~ in a branched oligomer
backbone; 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 l~ie~.~ll the average llUlllb~,. of moles of t'ne co,l~spo~ lg units per
mole of said ester and said ester has a molecular weight la~ing from about 500 to about
5,000.
Pl~,f~ d SEG and CAP lllGllOlllcl~ for the above esters include Na-2-(2-,3-
dihydro~yl,lol)oxy)e~ 1fonate ("SEG"), Na-2-~2-(2-hydroxyethoxy) ethoxy~
el?.~~~P~lfonate ("SE3") and its homologs and ll~iXlul~,S thereof and the products of
ethoxylating and sulru~ allyl alcohol. P~r~.l.,d SRA esters in this class include the
product of ll~ e~ iÇyi~l~ and oligo.ll~ in~5 sodium 2-{2-(2-
hydroxyethoxy)ethoxy}t;lh~ lfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-
~ ethoxy}ethoxy]eth~n~sTllfonate, DMT, sodium 2-(2,3~ ydlu~y~ opoxy) ethane sulfonate,
35 EG, and PG using an ~pl~>.iale Ti(IV) catalyst and can be (lesign~ted as
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44
(CAP)2(T)S(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -03S[CH2CH20]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~t~s 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 ~ se et ai; (II) SRA's with carboxylate le~".;i~l groups made by adding
trin~ litif~ anhydride to known SRA's to cull~el~ tel...i..~l hydroxyl groups to trimellitate
esters. With a proper selection of catalyst, the trimellitic anhydride forms linl~s to the
Ic~ Lals of the polymer through an ester of the isolated carboxylic acid of trim~llitir
anhydride rather than by o~.~i~ of the anhydride linkage. Either nonionic or anionic
SRA's may be used as starting materials as long as they have hydroxyl ttormin~l groups
which may be esterified. See U.S. 4,525,524 Tung et al.; (Il~ anionic terephth~l~te-based
SRA's of the ulcLllalle-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl
caprolactam) and related co-polymers with molloll.~rs such as vinyl pyrrolidone and/or
di,ll~Lhyl~minoethyl ~ , including both nonionic and cationic polymers, see U.S.4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from
BASF made, by ~l~rling acrylic monomers on to sulfonated polyesters; these SRA'sass~Ledly have soil release and anti-redeposition activity similar to known cellulose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl m~nom~rs such as
acrylic acid and vinyl acetate on to plo~ s such as caseins, see EP 457,205 A to BASF
(1991); (V~) polyester-polyarnide SRA's ~l~)alCd by condensing adipic acid, capr )~ t~m~
and polyethylene glycol, e~ ly for Ll~,aLi~ 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.
Clav Soil Removal/Anti-redeposition A~ents
The compositions of the present invention can also optionally contain water-soluble
30 ethoxylated amines having clay soil removal and antiredeposition plo~lLics. Grallular
dct~lg~;l.L collll)o~ilions which contain these compounds typically contain from 0.01 % to
10.0% by weight of the water-soluble ethoxylates amines; liquid de~ e~lL compositions
typically contain 0.01 % to 5% .
,
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The most plere~r~d soil release and anti-redeposition agent is ethoxylated tetraethylene-
pe~t~mine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898,
VanderMeer, issued July 1, 1986. Another group of ~ ,r~lled clay soil removal-
antiredeposition agents are the cationic compounds disclosed in Eurol~eal1 Patent
S Application 111,965, Oh and Go~PIinl~, published June 27, 1984. Other clay soil
removal/antiredeposition agents which can be used include the ethoxylated amine polymers
disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; t'ne
~will~lionic polymers disclosed in Eul~edll Patent Application 112,592, Gosselink,
publi~hed July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor,
issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in
the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160,
VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.Another type of pl~r~led antiredeposition agent inrh1-les the carboxy methyl cellulose
(CMC) materials. These materials are well known in the art.
1~
Polymeric Dis~e. ~ Agents
Polymeric ~lispe.~ , agents can advantageously be utilized at levels from 0.1% to 7%, by
weight, in the conl~osilions herein, especially in the pl~sellce of zeolite andl/or layered
silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates
and polyethylene glycols, although others know.,l in the art can also be used. It is believed,
tnough it is not inten-lPd to be limited by t'neory, that polymeric dis~l~.hlg agents e~h~ c
overall dele.~ ,L builder ~c~ru~ ce, when used in combil~lion with other builders
(inr.~ ing lower molecular weight polycarboxylates) by crystal grow~ i lhibi~n,
particulate soil release ~I;,,.I;.~n, and anti-redeposition.
Polymeric polycal'L,o~ylale materials can be prepared by polymerizing or copolyllle~ lg
suitable ul-salu~dted lllOllull.~,~S, preferably in their acid form. Unsalul~l~d monomeric
acids that can 'oe poly~ i~d to form suitable polymeric polycarboxylates include acrylic
acid, maleic acid (or maleic anhydlide), fumaric acid, itaconic acid, aconitic acid,
mesaconic acid, citraconic acid and methylenpnl~lonic acid. The presence in the polymeric
~ polycarboxylates herein or nlullolllelic segm~ontc~ cont~ining no carboxylate radicals such as
villy-lmelllyl ether, styrene, ethylene, etc. is suitable provided that such segments do not
co..~ P more than 40% by weight.
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46
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
S preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can
include, for example, the aLkali metal, al~ olliu.n and substituted ammonium salts.
Soluble polymers of this type are l~nown materials. Use of polyacrylates of this type in
d~,t~,~ e.lL compositions has been disclosed, for ~iull~lc, in Diehl, U.S. Patent 3,308,067,
issued March 7, 1967.
Acryliclmaleic-based copolymers may also be used as a pl~;r~l,ed compor~ent of the
di~ ing/anti-redeposition agent. Such materials include the water-soluble salts of
copolymers of acrylic acid and maleic acid. The average molecular weight of suchcopolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably
15 from 5,000 to 75,000, most preferably frorn 7,000 to 65,000. The ratio of acrylate to
m~ te Seg~ in such copolymers will generally range from 30:1 to 1:1, more
~,f,~ably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid
copolymers can in~ e~ for example, the aL~cali metal, ammonium and su~ uled
~mmonillm salts. Soluble a~lylaletm~ te copolymers of this type are known materials
20 which are described in Eulv~all Patent Application No. 66915, published Decemher 15,
1982, as well as in EP 193,360, published September 3, 1986, which also des-;lil~s such
polymers C~ iSill~ ydlv~y~lu~ylacrylate. Still otheruseful dispe~ g agents include
the maleiclacrylic/vinyl alcohol terpolymers. Such materials are also fli~cll~se~l in EP
193,360, inrl~ in~, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another poly~ .ic l.laL~ ial which can be inrl~ e-1 is polyeti~ylene glycol (PEG). PEG can
exhibit d;s~.sillg agent ~.r~ ce as well as act as a clay soil removal-all~ position
agent. Typical molecular weight ranges for these L~ul~oses range from 500 to 100,000,
preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.
Polyas~allal~ and poly~ te dis~l~ing agents may also be used, especially in
co-.j...-l lion with zeolite builders. Di~pe~ g agents such as polya~ preferably have
a molecular weight (avg.) of 10,000.
3~ Bri~htener
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47
Any optical brighteners or other bright~lling or w~ g agents known in the art can be
incorporated at levels typically from 0.01% to 1.2%, by weight, into the delelg~,.ll
compositions herein. Col~ lercial optical brighteners which may be useful in the present
S invention can be cl~sififAc~ into subgroups, which include, but are not nPce~s~ ily limited
to, derivatives of stilbene, pyr~oline, C~ , carboxylic acid, ~~ f~c)r~nines~
tliben7othiophene-5,5-dioxide, azoles, 5- and 6--..~ he~d-ring heterocycles, and other
mi~c~ nf ous agents. FX~ IÇS of such b.i~llte~ are disclosed in "The Production and
Application of Flu- l~,SCf lll Bri~ e.~in~ Agents", M. Zahradnik, Published by John Wiley
10 & Sons, New York (1982).
Specific e~ ,lcs of optical b~ .f l~ which are useful in the present compositions are
those i~lentified in U.S. Patent 4,790,856, issued to WLlcon on Decf ~ el 13, 1988. These
bri~ u1~includethePHORw~ll~;-seriesofbri~l~t~ s fromVerona. Other
15 bri~ nf 1~ disclosed in this l~fL.cllce include: Tinopal UNPA, Tinopal CBS and Tinopal
5BM; 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)-stilbenes; 4,4'-
bis(styryl)bi~hcllyls; and the aminocoul,~a"ns. Specific eY~mpl~s of these bri~ --- lS
include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(bc~.,;...iA~7Ol-2-yl)ethylene; 1,3-
diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-napthotl,2-d]oxazole;
and 2-(stilben4-yl)-2H-n~phth--[1,2-d]triazole. See also U.S. Patent 3,646,015, issued
February 29, 1972 to W~milt(~J~
Dye Transfer Inhibitin~ A~ents
The cc.",~ilions of the present hl~cl~lioll may also include one or more materials effective
for il~il~ili lg the lla~ of dyes from one fabric to another during the cle~ning process.
Generally, such dye Ll~r~l inhibiting agents include polyvinyl pyrrolidone polymers,
pOlyal~ N-oxide polymers, copolymers of N-villylpy,lolidone and N-vinylimi~l~7ole~
~ fSe phthalocyall e, peroxidases, and r,li~lulcs thereof. If used, these agents~pically col~ ise from 0.01% to 10% by weight of the composition, ~lcr~lably from
- 0.01% to 5%, and more ~l,Çc;lably from 0.05% to 2%.
More specifically, the polyamine N-oxide polymers plc~.lcd for use herein contain units
35 having the following structural formula: R-AX-P; wherein P is a poly,n~li,able unit to
_
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48
which an N-0 group can be ~tt~rh~ or the N-0 group can form part of the polymerizable
unit or the N-0 group can be attached 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 att~rh~ or the N-0 group is part of these groups. Preferred
pol~all ine N-oxides are those wh~.eill R is a heterocyclic group such as pyridine, pyrrole,
imi~ 701e, pyrrolidine, piperidine and derivatives thereof.
The N-0 group can be ~ esc:--Led by the following general structures:
(Rl)x--I--(R2)y; N--(Rlhc
(R3)z
wl~leil~ Rl, R2, R3 are ,~liph~tir, ar~ alic, heterocyclic or alicyclic groups or
colllbillalions thereof; x, y and z are 0 or 1; and the nitrogen of the N-0 group can be
15 , tt~h~-l or form part of any of the arol~mell~ioned groups. The an~ine oxide unit of the
polyalllille N-oxides has a pKa < 10, prè~erably pKa < 7, more ~ er~ ,d pKa < 6.
Any polymer bacl~olle can be used as long as the amine oxide polymer formed is water-
soluble and has dye Llal~sf~. inhibiting ~u~Lies. E~ ~lrs of suitablè polymeric
20 backbones are polyvhl~ls, polyalkylenes, polyesters, poly~ , polyamide, polyimides,
polyacrylates and ll~i~ ,s thereof. These pûlymers include random or block cûpolytners
where one monomer type is an amine N-oxide and the other IllOnUllle- type is an N-oxide.
The amine N-oxide polytners typically have a ratio of amine to the amine N-oxide of 10:1
to 1:1,Q00,000. However, the number of amine oxide groups present in ~e pOlyall~ille
25 oxide polymer can be varied by a~iu~lialt: copolyll~ aLion or by an dy~ idle degree
of N-o~ tion. The pOlydL~ c oxides can be obtained in almost any degree of
polymeli~aliull. Typically, the averâge molecular weight is within ~e range of 500 to
1,000,000; more preÇ~ d 1,000 to 500,000; most pler~ ,d 5,000 to 100,000. This
~rc~lled class of materials can be referred to as "PVNO".
,
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49
The most preferred polyamine N-oxide usefill in the dct~,~ell~ compositions herein is
poly(4-vhlyl~ylidine-N-oxide) which has an average molecular weight of 50,000 and an
amine to amine N-oxide ratio of 1:4.
.~
S Copolymers of N-villyl~yllolidone and N-vinylimi~l~7ole polymers (referred to as a class as
"PVPVI") are also ~l~fi .led for use herein. P~:r~ably the PVPVI has an average
molecular weight range from 5,000 to 17000,000, more preferably from 5,000 to 200,000,
and most preferably from 10,000 to 20,000. (The average molecular weight range is
dt;~ ed by light SCall~,~i~, as described in Bartb, et al., Ch~omir~l Analysis. Vol 113.
10 "Modern Methods of Polymer Characltli~alion", the disclosures of which are inc~,~o,aLt:d
herein by ,cif~ ce.) The PVPVI copolymers typically have a molar ratio of N-
vhlylilllidazole to N-vhlyl~llolidone from 1:1 to 0.2:1, more preferably 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
d
The present invention compositions also may employ a polyvi~ lolidone ("PVP")
having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to
200,000, and more L"efel~ly from 5,000 to 50,000. PVP's are known to ~.OllS skilled
in the dete~,e.ll field; see, for example, EP-A-262,897 and EP-A-256,696, inco,l,c,lalt;d
20 herein by ler ~el~ce. Compo~ilions cont~ining PVP can also contain polyethylene glycol
("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000
to 10,000. Preferably, t'ne ratio of PEG to PVP on a ppm basis delivered in wash solutions
is from ~:1 to 50:1, and more preferably from 3:1 to 10:1.
The deltlgell~ compositions herein may also optionally contain from 0.005% to 5% by
weight of certain types of hydrophilic optical bri~l-t~ which also provide a dye Iral~.f~.
inhibition action. If used, the compositions herein will preferably colll~lise from 0.01% to
1% by weight of such optical brigl.~r~
The ll~dl~hilic optical bri~l.t~ useful in the present invention are those having the
structural form~
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W 097/44433 PCTrUS97/08373
Rl R2
N O) I ~C=C~ I ~(N
R2 SO3M SO3M Rl
wlle~ Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl, R2 is
s~lec.te(l from N-2-bis-hydlo~y~Lllyl, N-2-hydroxyethyl-N-methylamino, morpllilino, chloro
5 and amino; and M is a salt-forming cation such as sodium or pot~ m
When in the above forrnula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation
such as sodium, the bri~ rl.- r is 4,4',-bisl(4-anilino-6-(N-2-b}s-hydroxyethyl)-s-triazine-2-
yl)amino]-2,2'-stilbellP~ lfonic acid and disodiurn salt. This particular bri~hten~r species
10 is cc~ ;ially ".~ f led under the tr~den~mP Tinopal-UNPA-GX by Ciba-Geigy
Corporation. Tinopal-UNPA-GX is ~Ae ~l~r~ ,d hydrophilic optical brightener useful in
the det~,lgellL compositions herein.
When in the above fonnula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M
is a cation such as sodium, the brigl,lr~ r is 4,4'-bis[(4-anilino-6-(N-2-l-ydlo~Ayethyl-N-
methylamino)-s-triazine-2-yl)amino]2,2 '-stilbenf ~ fonic acid disodium salt. TAhiS
particular bri~ species is cclllAIlf l~;ially marketed under the tra(lfen~mf Tinopal 5BM-
GX by Ciba-Geigy Corporation.
20 When in the above formula, Rl is anilino, R2 is morphilmo an~A M is a cation such as
sodium, tAhAe bri~ f~.f, is 4~4~-bis[(4-anilino-6-morphilAino-s-~ e-2-yl)amino]2~2~-
stilb~ fonic acid, sodium salt. This particular bright~n~r species is cullln~ ;ially
.n~.kelf~A under t~Ae tr~lc.)~ f Tinopal AMS-GX by Ciba Geigy ColAuol~tion.
25 The ~.~ecirlc optical bri~hl~n~,L species selçct~l for use in the present invention provide
especially effective dye Lldl~f~r inhibition performance benerlL~7 when used in cu,llbhA~Alion
with the select~l polymeric dye LA~AAk;f~ inhibiting agents h~leilAl~efore described. The
combination of such selectef1 polymeric mAaterials (e.g., PVNO and/or PVPVI) with such
selected optical bri~ ls (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal
30 AMS-GX) provides .~ignifir~ntly better dye transfer inhibition in aqueous wash solutions
than does either of these two delergelll composition components when used alûne. Without
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W O 97~44433 PCT~US97/08373
being bound by theory, it is believed that such brighlellel~ work this way because they have
high affinity for fabrics in the wash solution and thFler(,le deposit relatively ~uick on these
fabrics. The extent to which brightPn~rs deposit on fabrics in the wash solution can be
defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in
5 general as the ratio of a) the bri~l-lellel material deposited on fabric to b) the initial
bri~htr~ner concentration in the wash liquor. Bripl~ with relatively high exhAll~tion
co~rrlcie~ are the most suitable for inl~ibiLillg dye l-dl~rtl in the context of the present
invention.
10 Of course, it will be _~r~eiated that other, conventional optical brightPnPr types of
compounds can optionally be used in the present compositions to provide co..~.,l,lional
fabric "b~ .Fss" be~erll~, rather than a true dye ~ rt;l inhibiting effect. Such usage is
conventional and well-known to d~ ge~ll form~ ti~ns.
15 Che~ Agents
The delt;l2s~ compositions herein may also optionally contain one or more iron and/or
"-A-~ Pse chPl~tin~ agents. Such çhPl~tin~ agents can be selected from the groupc~ of amino carboxylates, amino phosphonates, polyfunctionally-~.,bs~ cl aro-
20 matic ch~ g agents and Illi~lur~s therein, all as hereinafter defined. Without inten-lin~
to be bound by theory, it is believed that the benefit of these materials is due in part to
their exceptional ability to remove iron and ...~-g~ se ions from w~shhlg solutions by
form~tion of soluble chPl~te~.
25 Amino carbo"yla~s useful as optional rhPl~ting agents include ethylel~e~ ace~ s,
N-hyd~(J~.,ll~lethylPn~li~...;...~l.;~ret~tPs, nitrilotri~ret~t~s, ethyle.~ i,....;l.r
L~L.d~ ionates, triethyle-~ rh -~ret~tPs~ diethyle~ n~p ~ rc~ les~ andethanoldigly~ s, allcali metal, ammonium, and ~l.sl;l~ l ammonium salts therein and
ll~i~lul~s therein.
Amino pho~ph~ s are also suitable for use as chPl~ting agents in the co---i)osilions of the
- invention when at least low levels of total phosphorus are pc~l.. iLIed in dcl~,g~ul
compositions, and include ethyle~ cis ~methyl~nPpho~yh~lldtes) as DEQUEST.
P~cÇell~d, these amino phosphonates to not contain allyl or aLI~enyl groups with more than
35 6 carbon atoms.
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52
Polyfunctionally-~u'bsLilul~d alollla~ic chP!~tin~ agents are also useful in the compositions
herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Pl~rellcd ~,
compounds of this type in acid form are dihydroxydisulfobe~ es such as 1,2-dihydroxy-
5 3,5-disulfo'oe,~ellc.
A p~ lcd biodegradable chelator for use herein is ethylenP~ minP di~ucci~
("EDDS"), ecpec;~lly the ts,s~ isomer as described in U.S. Patent 4,704,233, November
3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine rli~retir acid
(MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble
builders such as zeolites, layered silir~tPs~
If ~-tili7ed, these chto!~tin~ agents will generally comprise from 0.1% to 15% by weight of
the dt;~ lL compositions herein. More preferably, if lltili7P~ the rhPl~tin~ agents will
co~ i..e from 0.1 % to 3.0% by weight of such co~ o..ilions.
Suds Suy~ ssors
Ccllllpoullds for reducing or ~u~ressill~, the formation of suds can be incorporated into the
c~mrositi~nS of the present invention. Suds su~>~.,sion can be of particular importance in
the so-called "high co,-~e~ ;on cle~nin~ process" as desclibed in U.S. 4,489,455 and
4,489,574 and in front-loading Eulo~eau~-style washil~ m~r~inPs
A wide variety of materials may be used as suds .7u~pr~ssol~., and suds ~.Up~lC~Sois are well
known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia ofChPmir-~l Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One Cdt~,gOl ~ of suds ~.u~p,essor of particular interest enro...~ es monocarboxylic
fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued Scp~ll.b~l 27, 1960
to Wayne St. John. The monoc~.l,o~ylic fatty acids and salts thereof used as suds
~u~ .,ssor typically nave lrydlocalbyl chains of 10 to 24 carbon atoms, preferably 12 to 18
carbon atoms. Suitable salts include the aL~cali metal salts such as sodium, pol;-c~ .., and
lithium salts, and ammoniurn and aL~canolammonium salts.
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The dG~Glgelll 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 mollo~,alent alcohols, aliphatic
C1g-C40 ketones (e.g., ~Icalone), etc. Other suds inhibitors include N-aLkylated amino
S tri~ines such as tri- to hexa-aLt;ylm~ s or di- to tetra-aLkykliA...i..~ chlo~LI;a~ es
formed as products of ~;yàl~uliC chloride with two or three moles of a ~ laly or secondary
amine co,~ 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such
as monostearyl alcohol phosphate ester and monostearyl di-aL~cali metal (e.g., K, Na, and
Li) phosphates and phosph~At~ esters. The hydrocarbons such as ~arrm and halo~larr~
10 can be utilized in liquid form. The liquid hydrocarbons will be liquid at room te.ll~ela~ulc
and atmospheric pl~,SSUlG, and will have a pour point in the range of 40~C and 50~C, and
a ~--il.il,....~ boiling point not less thanllO~C (atmospheric ~lCS~ulc). It is also known to
utilize waxy hydroc~l,olls, preferably having a melting point below 100~C. The
hydrocal~onscol~liLulc a pr~f~,lGd caL~gOly of suds ~Upp,~s~Ol for dc~ ~lL
15 compositions. Hydrocarbon suds ~u~plc5S(j~ are described, for example, in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. The hydroca,l~o,ls, thus, include
aliphatic, alicyclic, al~,lllalic, and heterocyclic salulaled or ullsalu.dt~d hydlocA bul~s
having from 12 to 70 carbon atoms. The term "p~arrlll, " as used in this suds ~u~p,~ssor
ion, is int.-n~ d to include "~lui~s of true pa~arrL~Is and cyclic l~y~lloc&lbons.
Another p,Gf~ d càlGgoly of non-surfactant suds ~u~lcssors co~ ,ses silicone suds
~u~yleSSOrS. This Cal~ includes the use of polyorganosiloxane oils, such as
polydilllG~lylsiloxane, dis~,~ions or çm~ ions of polyo~ siloYAnP oils or resins, and
colll~hlalions of polyo,g~"t-~iloY~n~ with silica particles whelclu the polyorganosiloxane is
25 c~ o,Led or fused onto the silica. Silicone suds s-l~lcssors are well known in the art
and are, for e"~le, ~ close~ ~n U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo
etaland Eur~all PatentApplicationNo. 89307851.9, publishedrebl~ 7, 1990, by
Starch, M. S.
Other silicone suds su~l~s~r~ are disclosed in U.S. Patent 3,455,839 which relates to
compositions and processes for d~fOa~ lg aqueous solutions by incorporating therein small
amoull~ of polydi.ll.,lhylsiloxane fluids.
Mixtures of silicone and sil~n~tçfl silica are described, for i..~ re, in German Patent
Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular
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54
detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S.
Patent 4,652,392, l'~gincl~i et al, issued March 24, 1987.
An exemplary silicone based suds ~ul~ressor for use herein is a suds ~u~ies~ g amount
S of a suds controlling agent conei~tin~ essentially of:
(i) polydimethylsiloxane 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
composed 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 pl~fe~led silicone suds su~ressor used herein, the solvent for a continl~ol~s phase is
15 made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers
or ~uLLulcs thereof (~l~,f~ ,d), or poly~-~ylene glycol. The primary silicone suds
~u~ ssor is bldl-ched/crosslink~l and preferably not linear.
To illustrate this point further, typical liquid lau~ / deL~l~ enl compositions with
20 controlled suds will optionally comprise from about 0.001 to about 1, preferably from
about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said
silicone suds su~p~cssor, which col~ es (1) a nonaqueous emulsion of a yl~llaly
allliÇ.~ agent which is a llli~lUl~ of (a) a polyorganosiloxane, (b) a lesinous siloxane or a
silicone resin-producitu~ silt~-on~ compound, (c) a finely divided filler material, and (d) a
25 catalyst to promote the l.,~,lio~ of ll-i~lul~ components (a), (b) and (c), to form sil~nc l~tPs;
(2) at least one nonionic silicone ~ulr~ll, and (3) polyethylene glycol or a copolymer of
polyethylene-poly~lu~ylene glycol having a solubility in water at room t~pc,alul~ of
more than about 2 weight %; and willl~JuL poly~ro~ylene glycol. ~imilar ~ 0~ can be
used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued
Decc~.. 1~l 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et
al., issued re~l~y- 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 conl~lises polyethylene glycol and a
35 copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular
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WO 97~4~433 PCT~US97108373
weight of less than about 1,000, preferably between about 100 and 800. The polyethylene
glycol and polyethylene/polypropylene copolymers herein have a solubility in water at
room le~ .e,dLuie of more than about 2 weight %, preferably more than about 5 weight %.
S The ~.r~fell~,d 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
between 200 and 400, and a copolymer of polyethylene glycol/poly~ ylene glycol,
preferably PPG 200/PEG 300. Pl~,f~ ,d is a weight ratio of ~l~ ,cll about 1:1 and 1:10,
most ~ felably '~.wcc~ 3 and 1:6, of polyethylene glycol:copolymer of polyethylene-
10 poly~.lo~ylene glycol.
The ~rcLI.~d silicone suds ~u~Lessors used herein do not contain poly~lo~.ylene glycol,particularly of 4,000 molecular weight. They also preferably do not contain block
copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds ~u ~leSSOl~. useful herein coll~.ise the secondary alcohols (e.g., 2-aL~cyl
aL~canols) and llliALu~es of such alcohols with silicone oils, such as tne silicones disclosed in
U.S. 4,798,679, 4,075,118 and EP 150,872. The secondar,v alcohols include the C6-C16
aLtcyl alcohols having a Cl-C16 chain. A p~crclrcd alcohol is 2-butyl octanol, which is
20 available from Condea under the tr~d~om~rk ISOFOL 12. Mixtures of secondary alcohols
are available under the tr~1em~rk ISALCHEM 123 from Fnirh.om Mixed suds
~U~t~tl.,Ssol~ typically co.~.ise n~L~Llules of alcohol + silicone at a weight ratio of 1:5 to
5:1.
25 For any dclC~cllL compo~hir~n~ to be used in aulomalic laundry or dishwashing m~rhinPs,
suds should not form to the extent that they either overflow the washing m~rhin~ or
ne~;ali-/ely affect the washi~ rçh~ u~ of the dishwasher. Suds ~.u~.lcssors, when
ili7rd, are preferably present in a "suds ~tU~lCSsillg amount. By "suds ~.u~rc~
~m- -nt" is meant that the formulator of the composition can select an amount of this suds
30 controlling agent that will ~ rr.r~ y control the suds to result in a low-sndsing laundry or
dishwashing dcler~el~ for use in autom~tir laundry or dish~a~ g m~rhin~s.
The compositions herein will generally comprise from 0% to 10% of suds ~u~pl'essor.
When utilized as suds ~u~3~ressors, monocarboxylic fatty acids, and salts therein, will be
35 present typically in amounts up to 5%, by weight, of the deL~gt;lll composition.
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Preferably, from 0.5% to 3% of fatty monocarboxylate suds ~,upplessor is l~tili7ed
Silicone suds suppressors are typically utilized in ~mo~lntc up to 2.0 %, by weight, of the
deLc.g~llt composition, although higher amounts may be used. This upper limi~ is practical 7
in nature, due primarily to concern with keeping costs minimi7-od and effectiveness of
Slower amounts for effectively controlling s~3~iCin~. Preferably from 0.01 % to 1 % of
silicone suds su~ ssor is used, more preferably from 0.25 % to 0.5%. As used herein,
these weight pel~;enL~ge values include any silica that may be utilized in combination with
polyorganosiloxane, as well as any optional materials that may be ~ltili7P~l Monostearyl
phosphate suds ,u~r~ssors are generally utilized in a n~un~ y,illg from 0.1 % to 2 %, by
10weight, of the composition. Hy~ c~on suds ~,u~ple,sors are typically utilized in
amounts ranging from O.Ol % to 5.0 % , although higher levels can he used. The alcohol
suds ~7U~ Ssol., are typically used at 0.2%-3% by weight of the fini~hPd compositions.
Alkoxylated Polycarboxylates
AL~coxylated polycarboxylates such as those ~ al.,d from polyacrylates are useful herein
to provide additional grease removal ~Ir~ ce. Such materials are described in WO91/08281 and PCT 90/01815 at p. 4 et seq., hlcol~ aled herein by r~felel~cc.
~h~mira1iy, these materials co~ ise polyacrylates having one ethoxy side-chain per every
7-8 acrylate units. The side-chains are of the formula -(CH2CH20)m(CH2)nCH3 wherein
m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to
provide a "comb" polymer type st~ucture. The mo1ecn1~r weight can vary, but is typically
in the range of 2000 to 50,000. Such alkoxylated polycall,o~ylates can colllp.ise from
0.05% to 10%, by weight, of ~e compositions herein.
Fabric S~r~n~.~
Various through-the-wash fabric sor~-l~.;" especi~tly the imp~lra~le ~n~ clays of U.S.
Patent 4,062,647, Storm and Nirschl, issued Dec~,.n~l 13, 1977, as well as other sorLen~,
clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by
weight in the present compositions to provide fabric sor~el~r bencrll~ co~;u~ lly with
fabric cle lnin~. Clay softeners can be used in combillalioll with amine and cationic
softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983
and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981
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Pcl rull~es
Perfumes and perfumery ingredients usefill in the present compositions and processes
comprise a wide variety of natural and sylllllcLic chPmir~l ingredients, including, but not
limited to, aldehydes, ketones, esters. Also included are various natural extracts and
essences which can C~ pliSe complex mixtures of ingredients, such as orange oil, lemon
oil, rose extract, lavender, musk, patchouli, b~ mir essence, sandalwood oil, pine oil,
cedar. Finished pe.rullles can comprise extremely complex ~l~i~lul~s of such ingredients.
Pinished perfi~mes typically comprise from 0.01% to 2%, by weight, of the de~cl~elll
compositions herein, and individual pe.rul"~y ingredients can conl~lise from 0.0001% to
90% of a finich~d pe.Çu,lle composition.
Non-limitin~ examples of ~.ru",e ingredients useful herein include: 7-acetyl-
1,2,3,4,5,6,7~8-octahydro-1,1,6~7-~cL~ yl n~phth~lenf; ionone methyl; ionone gamma
methyl; methyl cedrylone; methyl dil,y-l,oja~",onate; methyl 1,6,10-llh~lclllyl-2,5,9-
cycl~odec~lliell-l-yl ketone; 7-acetyl-1,1,3,4,4,6-h~nclllyl t~tr~lin; 4-acetyl-6-tert-
butyl-l,l-d",.cll,yl indane; para-hydroxy-phenyl-l,uLa"o~e; benzophenone; methyl beta-
naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hf~x~ l.yl indane; 5-acetyl-3-isopropyl-1,1,2,6-
leL~an,cll,yl indane; l~odec~n~l, 4-(4-hy~llv~y4-lllelllyl~elllyl)-3-cyclohexene-l-
carboxaldehyde; 7-llylllo~y-3,7-di"l~lhyl oc~t~n~l; 10-lln-lrcen-1-al; iso-hexenyl cyclohexyl
carboxaldehyde; formyl tricyclodecane; contlf nc~tion products of hydro~ycill~,nellal and
methyl a"~ ilate, con~n.~ti~n products of hydroxycitronellal and indol, CO~ f n~lion
products of phenyl aret~l~1ehyde and indol; 2-methyl-3-(para-tert-butylphenyl)-
~v~;ol~ldehyde; ethyl vanillin; heliotropin; hexyl ci.~ ...ir aldehyde; amyl cil~n~...ir
25 aldehyde; 2-methyl-2-(para-iso-~ ylphenyl)-propionaldehyde; c(Jull~in; ~3ee~ tone
g~mm~; ~;yelopc~ lec~nolide; 16-hydroxy-9-h~oy~lf c~nnic acid lactone; 1,3,4,6,7,8-
hexahydro-4,6,6,7,8,8-h~ ."l Ihylcyclopenta-gal[nma-2-bcl~opy~e; beta-n~rhthol methyl
ether; ambroxane; ~ c~hydro-3a,6,6,9a-tetramethylnaphtho[2,1b]filran; cedrol, 5-(2,2,3-
trimethylcyclopent-3-enyl)-3-,l,~;ll,yl~l,L7~l-2-ol; 2-ethyl4-(2~2~3-lli,llcLhyl-3~yclope~ n
30 yl)-2-buten-1-ol; ca,~ophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl
acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.
Particularly pre~"~d ~elfulllc materials are those that provide the largest odor~ improvements in fini~hr~ product co~ o~iLions cont~inin~ cr~ os. These perfumes
35 include but are not lirnited to: hexyl ci.".,.."ir. aldehyde; 2-methyl-3-(para-tert-
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58
butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl
n~phth~lene; 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-
S hexahydro~,6,6,7,8,8-h~ yl-cyclopenta-gamma-2-b~l-2~yrane; do~1e~hydro-
3a,6,6,9a-tetram~lh~ htho[2,1b]furan; ani~klehyde; counlalill; cedrol; vanillin;cyclopent~ oc~nolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.
Other perfume m~tt~ri~l~ include P~sçnti~l oils, resinoids, and resins from a variety of
10 sources including, but not limited to: Peru balsam, Olih~n-lm resinoid, styrax, l~ nllm
resin, nu~neg, cassia oil, bel~o..l resin, coriander and lavandin. Still other ~lru lle
ch~mi~ include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol,
2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as
di~ yll h~ te can be used in the fini~hed ~"runlc culll~osiLions.
C)ther Ingredients
A wide variety of other hlyred;~ s useful in d~t~lgelll compositions can be in~ de~l in the
colllposilions herein, inrhl-lin~ other active illgr~.lit;ll~, carriers, hydloL,~l,es, proce~ing
20 aids, dyes or pigmPntc, solvents for liquid formulations, solid fillers for bar compositions,
etc. If high sudsing is desired, suds boosters such as the Clo-C16 alkanolamides can be
incorporated into the compositions, typically at 1%-10% levels. The C1o-C14
monoeth~n-)l and ~lieth~nol amides i11l~str~t~ a typical class of such suds boosters. Use of
such suds boosters with high s~ cin~ optional surf~t~nt~ such as the amine oxides,
25 betaines and slllt~in~s noted above is also advantageous. If desired, water-soluble
m~-~sj.. and/or calcium salts such as M~C12, MgSO4, CaC12 CaS04, can be added atlevels of, typically, 0.1~o-2%, to provide additional suds and to el h~re grease removal
~.rO~ lce.
30 Various dt:hr~ive ingredients employed in the present colll~osiliolls optionally can be
further stabilized by absoll,hlg said ingredients onto a porous hyd~hobic substrate, then
coating said substrate with a hydlophobic coating. Preferably, the dctelsive ingredient is
atlmixed with a ~ulrh~;~nl before being absorbed into the porous ~ul~sLl~le. In use, the
detel~ive ingredient is released from the ~ul)sLlale into t~e aqueous washing liquor, where it
35 ~ s its int~n~led det~.~ive function.
_
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59
To illustrate this t~chni~e in more detail, a porous hydrophobic silica (tr~cleIn~rk
SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~ining 3%-
5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, tne
5 enzyme/surfactant solution is 2.5 X the weight of silica. The res~llting powder is dispersed
with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can
be used). The resll1~in~ silicone oil dispersion is em~ ifi~l or otherwise added to the final
dele.~ellL matrix. By this means, ingredients such as the aforementioned el.~.yllles,
bl~ ~h~os, bleach activators, bleach catalysts, photoacLi~lal~,ls, dyes, fluorescers, fabric
10 conditioners and hydrolyzable surf~l~t~nt~ can be "proLecléd" for use in deL~,ge,lLs,
in~ in~ liquid laundry det~rgell~ compositions.
Liquid delGrgGIlL compositions can contain water and other solvents as calliel~. Low
molecular weight primary or seCorUl~ry alcohols exemplified by .~ h~-lol~ ethanol,
15 ~r~)allOI, and iSu~ pallOi are suitable. Monohydric alcohols are p,Gfel,2d for solubilizing
surfactant, but polyols such as those c~ nt~inin~ from 2 to 6 carbon atoms and from 2 to 6
hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycGlil~, and 1,2-pç~allediol)
can also be used. The col~osilions may contain from 5% to 90%, typically 10% to 50%
of such ca"i~
The d~lclgenL culllL,osilions herein will preferably be formlll~ted such that, during use in
aqueous cle~ning o~,aliol~, the wash water will have a pH of b~ l 6.5 and 11,
~lert;~ably b~L-.~n 7.5 and 10.5. Liquid dishwashing product formlll~tir~ns p,~rt;,dbly
have a pH b.,.~,c., 6.8 and 9Ø Laundry products are typically at pH 9-11. Techni-llles
for controlling pH at lcc~,.. rntl~ usage levels include the use of buffers, aLkalis, acids,
etc., and are well known to those skilled in the art.
Granules ~....r~
Adding the bis-aL~oxylated cationics of this invention into a crutcher mix, followed by
conventional spray drying, helps remove any residual, potentially malodorous, short-chain
~ amine co~ J~ i. In the event the formulator wishes to p,~ale an ~-lmix~hle particle
CU--~ g ~he alkoxylated c~tio~i~s for use in, for example, a high density granular
dct~.~,t;lll, it is pçer~ d that the particle composition not be highly ~lk~lin~. Processes for
~l~p~ing high density (above 650 g/l) gr~mllPs are described in U.S. Patent S,366,652.
,
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Such particles may be fonmll~tP~l to have an effective pH in-use of 9, or below, to avoid
the odor of i~ ul;ly amines. This can be achieved by adding a small amount of acidity
source such as boric acid, citric acid, or the like, or an a~lopriate p~I buffer, to the
particle. In an alternate mode, the prospective problems associated with amine malodors
5 can be masked by use of perfume ingredients, as disclosed herein.
Examples
The following e~ les are illustrative of the present invention, but are not meant to limit
or otherwise define its scope. All parts, p~l~e.lL~ges and ratios used herein are ~ cssed
10 as percent weight unless otherwise specified.
In the following examples, the abbreviated component ident~ tions have the following
mP.,. " j "~
LAS : Sodium linear C12 aLkyl benzene sulfonate
TAS : Sodium tallow aL~cyl sulfate
C45AS : Sodium C14-Cls linear aL~cyl sulfate
CxyEzS : Sodium Clx-C1y ~ uhed aLtcyl sulfate
co~-len~ec~ with z moles of ethylene oxide
C45E7 : A C14 15 predu.. i~ y linear p~ ~y
alcohol con~1eI-~ed with an average of 7 moles
of ethylene oxide
C25E3 : A C12 15 branched plilllaly alcohol
con-l~n~ed with an average of 3 moles of
ethylene oxide
C25E~ : A C12 15 branched p~ ~y alcohol
con~len~ed with an average of 5 moles of
ethylene oxide
CocoEO2 : Rl.N+(cH3)(c2H4oH)2 WithRl = C12 ~
cl4
Soap : Sodium linear aL~cyl carboxylate derived from
an 80/20 ~ ur~ of tallow and coconut oils.
TFAA : C16-C1g alkyl N-methyl ~ c~mirle
TPK~A : C12-C14 topped whole cut fatty acids
STPP : An~ydrous sodium tripolyphosphate
Zeolite A : E~ydrated Sodium ~ minosilicate of formula
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61
Nal2(A102SiO2)12. 27H20 having a ~lill~l~
particle size in the range from 0.1 to 10
micrometers
- NaSKS-6 : Crystalline layered silicate of ~ormula
~-Na2Si2Os
Citric acid : Anhydrous citric acid
Ca,l,onaL~ : Anhydrous sodium carbonate with aparticle
size bclw~ 20011m and 900~1m
Bicarl,ol~s.le : Anl~yd~ous sodium bicarbonate with a particle
size distribution belweell 400~1m and 1200~1m
Silicate : Amorphous Sodium Silicate (SiO2:Na20; 2.0
ratio)
Sodium sulfate : Anhydl(,us sodium sulfate
Citrate : Tri-sodium citrate dihydrate of activity- 86.4%
with a particle size disL~ibulion bel~e~,n
425,um and 850 ,um
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average molecular weight 70,000.
CMC : Sodium carbo~yllltll-yl cçlll-lose
E~o~dse : Proteolytic cl~yllle of activity~ 4KNPU/g sold
by NOVO Industries A/S under the traflen~mP
Savinase
Alcalase : Proteolytic ~,l~yllle of activity 3AU/g sold by
NOVO Industries A/S
C~ JI~e : Cellulytic cl~ylllc of activity 1000CEVU/g
sold by NOVO InLlu~ s A/S under the
tr~ Pn~m~ C~ y~
Amylase : Amylolytic enzyme of activity 60KNU/g sold
by NOVO Industries A/S under the tr~l.on~nP
T~ l~llyl 60T
Lipase : Lipolytic e1ILY111C of activity 100kLU/g sold
by NOVO Tn~ es A/S under the tr~ Pn~mP
Lipolase
P.nrlol~e : Endoglunase enzyme of activity 3000
CEVU/g sold by NOVO In~u~Llics A/S
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62
PB4 : Sodium perborate tetrahydrate of nominal
for~nula NaE?o2.3H2o H2o2
PB1 : Anhydrous sodium perborate bleach of ,~
nominal formula NaB~2-H2~2
S Percarbonate : Sodium Pe,c~ ollate of nominal formula
2Na2C03-3H202
NOBS : Nonanoylo~yl~e~ e sulfonate inthe form of
the sodium salt.
TAED : Tetraacetylethyle~-P~
NACA-OBS : (611OI~ . caproyl) o~y~ ne
sulphonate
DTPMP : Diethylene triamine penta (methylene
phosphonate), Illalhtled by Monsanto under
the Trade name Dequest 2060
Co Catalyst : pent~minP acetate cobalt (III) salt
Mn Catalyst : MnIV2(m-0)3(1,4,7~ ,lc~,yl-1,4,7-
triazacyçlo...,.~.F)2-(PF6)2as described in
U.S. pat. nos 5 246 621 arld 5 244 594
Photoactivated : Sulfonated Zinc Phthalocyanine e
in bleach dextrin soluble polymer
Brightener 1 : Disodium4,4'-bis(2-sulphostyryl)biphenyl
Bright~nPr 2 : Disodium4,4'-bis(4-anilino-~-morpholino-
~.3.5-triazin-2-yl)amino) stilhenP-2:2
disulfonate.
HEDP : I,l-hydroxye~ ule flil.ho~,~hol2ic acid
PVNO : PolyvillylL"rlidine N-oxide
PVPVI: Copolymer of poly~ ,yl~llolidone and
viny1imiA~7.01e
SRA 1: Sulrub~ yl end capped esters wi~
oxyethylene oxy and l~ hLllaloyl backbone
SRA 2 : Diethoxylated poly (1, 2 propylene
~ tP) short block polymer
Silicone antifoam: Polyd,l~ llyl~ n~ fo~m con~oller wi~
siloxane-oxyaL1cylene copolymer as di~l~.ing
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63
agent with a ratio of said foam controller to
said di~e~ g agent of 10:1 to 100:1.
In the following Examples all levels are quoted as % by weight of the composition.
s
EXAMPLE I
The following delelg~lll form~ tions according to the present invention are ~ aL~d,
where A and C are phosphorus-co~ dct~ge~l co--l~osiLions and B is a zeolite-
COI-l;~ , dct~ ,elll coll",~silion.
A B C
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45 A S 8.0 5.0 11.0
M A/A A 2.0 4.0 2.0
~ L A S 6.0 8.0 11.0
TAS 1.5 - -
CocoMeEO2* 1.5 1.0 2.0
Silicate 7.0 3.0 3.0
C M C 1.0 1.0 0.5
Bri~ht~n~r 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
D TP M P 0.4 0.4 0.2
Spray O n
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone ~Liroau~ 0.3 0.3 0.3
r~r ~ .c 0.3 0.3 0.3
I~ry additives
Caubo,Lale 6.0 13.0 15.0
PB4 18.0 18.0 10.0
- PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Mn Catalyst 0.3 0.05 0.4
Photoactivated bleach 0.02 0.02 0.02
,
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64
Protease 1.0 1.0 1.0
Lipase 0 4 0 4 0 4
Amylase 0.25 0.30 0.15 ?
Dry mixed sodium sulfate 3.0 3.0 5.0
S Balance (Moisture &
Miscellaneous) To: 100.0 100.0 100.0
Density (g/litre) 630 670 670
*The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an
equivalent amount of any of ~u~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
10 sllrf~t~ntc herein.
EXAMPLE II
The following dt:L~lg~ formulations, according to the present invention are ~l~ared:
G H
Blown Powder
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 13.0 11.0 21.0
C45AS 8.0 7.0 7.0
CocoMeEO2* 1.0 1.0 1.0
Mn Catalyst 0.9 0.7 0.05
Silicate - 1.0 S.0
Soap - - 2.0
Bri~ .-, 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
DFPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Pr~)t~se 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
~mylase 0.1 0.1 0.1
3s Cell~ e 0.1 0.1 0.1
,
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NOBS - 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfate - 6.0
R~1~nre (Moisture
S & Mi~cell~n~ous~ To: 100 100 100
*The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an
equivalent amount of any of surf~rt~nt~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~ct~ntc herein.
EXAMPLE m
The following high density and bleach-co..l;~ leh~ t form~ tions, accor~i~g to the
present invention are l~l~c;d:
K L
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 0.4 0.4 0.4
MA/AA 4Ø 2.0 2.0
~ggk~..,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
Carbonate 8.0 8.0 4.0
Spray On
P~ru~e 0.3 0.3 o 3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
- Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Call~ al~; 8.0 15.0 10.0
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66
TAED 6.0 2.0 5.0
PB1 13.0 7.0 10.0
Mn Catalyst 0.02 0.4 0.1
Polye~hylene oxide 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
Cell~ ce - 0.6 0.6 0.6
Silicone allLir~ 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
nre (Moisture &
Miscellaneous) To: 100.0 100.0100.0
Density (g/litre) 850 850 850
*The bis-AQA-l (CocoMeEO2) surfactant of the Example may be replaced by an
equivalent amount of any of sul r~ bis-AQA-2 through bis-AQA-22 or other bis-AQA
s~ rt~nt~ herein.
EXAMPLE IV
The following high density det~ L formulations according to the present invention are
l'l~p~d:
2~ M N
Blown Powder
Zeolite A 2.5 2.5
Sodium sulfate 1.0 1.0
CocoMeEO2* 1.5 1.5
30 ~gl-- ,aLe
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Ca l,ol~te 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
-
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67
DTPMP 0.4 0.4
Spray On
r~e C25E5 5-0 ~-~
Perfume 0 5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5-0 7.0
Percarbonate 15.0 15.0
Mn Catalyst 0.03 1.4
SRA 1 0.3 0.3
l?~ut~dse 1.4 1.4
Lipase 0.4 0.4
~e~ e 0.6 0.6
Amylase 0.6 0.6
Silicone a,~ . 5.0 5.0
B~ r-.. ~ 1 0.2 0.2
Bright~n~r 2 0.2
R~l~n~e (Moisture &
Miscellaneous) To: 100 100
Density (g/litre) 850 850
*The bis-AQA-l (CocoMeEO2) s-~- r;..il~-.l of the Example may be replaced by an
equivalent ~m~) lnt of any of surf. ~-t~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
25 s~lrf~t~nts herèin.
Any of the granular d ~r~.,.ll co,l,~osiliv"s provided herein may 'oe tabletted using known
tabletting m~th~s to provide d~,t~ tablets.
30 Modern ~ u---~ r disllwaslli~g d.,t~l~ C~ . can contain bl~rhin~ agents such as
hypochlorite sources; perborate, pel.;arl,o~ . or persulfate bl~rl~s; e~y~les such as
pl~dses, lipases and arnylases, or ~ Ul~S thereof; rinse-aids, especially n( niollic
surf~t~ntc; builders, in~lul1ing zeolite and phosphate builders; low-sudsing del~l.iv~
surf~rt~ntc, ecpec i~lly ethylene oxide/propylene oxide conll~n~t~os. Such compositions are
35 typically in the form of granules or gels.
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68
The following Examples A and B further illustrate the invention herein with respect to a
granular phosphate-cont~inin~ au~olllaLic dishwashing delcrge,ll.
S EXAMPLE V
% by weight of active material
INGREDIENTS A B
STPP (allhydlvus)1 31 26
Sodium Carbonate 22 32
Silicate (% Si~2) 9 7
Surfactant (nonionic) 3 1.5
NaDCC Bleach2 2 --
bis-AQA-1* 0.5 1.0
Sodium Perborate 7.79 5
lS TAED -- 1.5
Co Catalyst 0.2 0.2
Savinase (Au/g) -- 0.04
T~ yl (Amu/g) 425
Sulfate ~ 25
r~,.rulllc/Minors to 100% to 100%
1Sodium tripolyphosphate
2Sodium dichloro~;y~ul~dt~
*The bis-AQA-1 ~ulr~cL~ll can be lcplaced by bis-AQA-2 through bis-AQA-22.
XAMPLE VI
The following illu~LIdt s ll.i~Llul~s of bis-AQA s~ rt~nt~ which can be sv~ tecl for the
bis-AQA suff~ct~nt~ listed in any of the fol~ oi~ F~ S. As disclosed hereinabove,
such u~i~-lul~,S can be used to provide a s~e~;Lluul of ~eLrolll~ce ~n~~ and/or to provide
cle~nin~ colll~osi~iol~s which are useful over a wide variety of usage conditions.
30 E~.,felably, the bis-AQA surf~t~nt~ in such ll~LY~Lulcs differ by at least 1.5, preferably 2.5-
20, total EO units. Ratio ranges (wt.) for such n~ ulcs are typically 10:1-1:10. Non-
lim-ti~ c~ CS of such l~lU-t;s are as follows.
Components Ratio (wt.)
35 bis-AQA-1 + bis-AQA-S 1:1
,
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69
bis-AQA-l + bis-AQA-10 1:1
bis-AQA-l + bis-AQA-15 1:2
bis-AQA-1 + bis-AQA-5
- ~ bis-AQA-20 1:1:1
5bis-AQA-2 + bis-AQA-5 3:1
bis-AQA-5 + bis-AQA-15 1.5:1
bis-AQA-1 + bis-AQA-20 1:3
10 Mixtures of the bis-AQA surfq-~t~ t~ herein with the corresponding eqtio~ s ~rfq-~tqn~
which contain only a single ethoxylated chain can also be used. Thus, for eY~mrle,
~Ul~S of ethoxylated cationic surf~tqnt~ of the fo~nula RlN+CH3[EO]x~EO]yX~ and
R1N+(CH3)2~EO]zX-~ wll~le.l~ R1 and X are as disclosed above and wh.,.cil7 one of the
CaLiOlliCS has (x+y) or z in the range 1-5 ~ cf~.dbly 1-2 and the other has (x+y) or z in the
range 3-100, preferably 10-20, most p.~r~,làbly 14-16, can be used herein. Such
c~ o~ilions advantageously provide illl~r~ved dct,Lgc.l~;y ~Ir~ al~e (especiqlly in a
fabric laUJ~ context) over a broader range of water ha~dncss than do the cqtioniC
surfactants herein used individually. It has now been ~lisc-J~cled that shorter EO cqtionirs
(e.g., EO2) illl~ ]VC the cl~-q-ning pelru~ nre of anionic ~ulr~ in soft water, whcleas
20 higher EO cationics (e.g., EO15) act to improve hardness to~erance of anionic surfactants,
thereby improving the cle~ning ~clr(J....~ e of anionic surf~ct~ntc in hard water.
Convention~l wisdom in the d_t~,lg~ y art suggests that b~ er.~ can ~Lilni~e the~clro~ n~e "window" of anionic sulrac~lb. Until now, however, bro~ ning the
window to ellco~ ass es~ ly all conditions of water hal~"ess has been i~o~ lc to25 achieve.
EXAMPLE VII
The following i11..~ s ~ luiCS of conventional non-AQA ~u~r~c~ which can be usedin co~ alio,l with the bis-AQA ~. r~cl~ in any of the foregoing Examples, but is not
30 i,.l~n-led to be li--.i~ thereof. The ratios of non-AQA ~. rh. ~ in the Illi~lul~s are
noted in p~s by weight of the surfactant l~lul~s.
Mixtures A-C
Ingredients Ratios
AS*/LAS 1: 1
AS/LAS 10:1 ~pref. 4:1)
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AS/LAS 1:10 (pref. 1:4)
*In the foregoing, the primary, s~k~ y linear AS surfactant can be replaced by an
equivalent amount of secondary AS or branched-chain AS, oleyl sulfate, and/or ~ cLur~S r~
thereof, including mixtures with linear, primary AS as shown above. The "tallow" chain
5 length AS is particularly usefill under hot water conditions, up to the boil. "Coconut" AS
is pl~felled for cooler wash ten~,laLules.
The mixtures of aL~cyl sulfate/anionic sulr~ nts noted above are modified by incorporating
a nonionic non-AQA ~ulr~ therein at a weight ratio of ar~ionic (total) to nonionic in the
range of 25:1 to 1:5. The nonionic surfactant can cv~ ise any of the collv~ ion~l classes
of ethoxylated alcohols or aLkyl phenols, alkylpoly~lycosides or polyhydroxy fatty acid
amides (less ~ief~ d if LAS is present), or Il~ibL~ul~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 secolldaly, branched or oleyl AS as noted above.
The ll i~lul~s of AS/AES noted above can be modified by incoll,uldtillg LAS therein at a
weight ratio of AS/AES (total) to LAS in the range from 1:10 to 10:1.
The l"-~Ul~S of AS/AES or their resl~ltin~ AS/AES/LAS n~ ul~,s can also be combined
25 with nonionic sl~r~At~nt~ as noted for Mixtures A-C at weight ratios of anionic (total) to
nonionic in the range of 25:1 to 1:5.
Any of ~e fo~g~ g ~ lul~s can be modified by the incorporation therein of an amine
oxide surfactant, wherein the amine oxide co~ ises from 1% to 50% of the total
30 surfactant llli~lUl'~,.
Highly ~l~fe~l~d combinations of the foregoing non-AQA ~ulr;~ will c~ e from 3%
to 60%, by weight, of the total ~michto(l laundry det~.gell composition. The fini~hPA
compositions will preferably c~."l~lise from 0.25% to 3.5%, by weight, of the bis-AQA
35 surfactant.
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EXAMPLE VIII
This Example illu~l,ales perfume fonm-lAtions (A-C) made in acc~ lance with the
invention for incorporation into any of the foregoing Examples of bis-AQA-c~
5 d~ ellL compositions. The various ingredients and levels are set forth below.
(% Wei~ht)
Perfume In~redient A B C
Hexyl C;nI1A~ aldehyde 10 0 - 5.0
2-me~yl-3-(para-tert-*ulyl~h~llyl)-propionaldehyde 5.0 5.0
7-acetyl-1,2,3 ,4,5,6,7,8-octahydro-1, 1,6,7-
A~ lt~yl l~ onp 5.0 10.0 10.0
Benzyl salicylate 5.0
7-acetyl-1,1,3,4,4,6-h- ~A~ y~ alin 10.0 5.0 10.0
Para-(tert-butyl) cyclohexyl acetate 5.0 5.0
Methyl dihydro j~ 5.0
Beta-napthol methyl ether - 0.5
Methyl beta-na~ llyl ketone - 0.5
2-methyl-2-(para-iso-propylphenyl)-propionaldehyde - 2.0
1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-h~ 1"~. Ihyl
cyclo~ll~-gamma-2-bel~o~y~ e - 9.5
Dodec~hydro-3a~6~6~9a-~~ lylllaphLllo-
[2, lb]furan - - 0.1
,Ani~ql-1ellyde - - 0 5
C~ . ;............................... . - - 5.0
Cedrol - - 0.5
Vanillin
Cyclop~ ec~ lide 3.0 - 10.0
Tricyclod~.,yl acetate - - 2.0
LaWa,luul resin - - 2.0
30 Tricyclodccellyl ~lu~io~a~ - - 2.0
Phenyl ethyl alcohol 20.0 10.0 27.9
Terpineol 10.0 5.0
Linalool 10.0 10.0 5.0
Linalyl acetate 5.0 - 5.0
Geraniol 5.0
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72
Nerol - 5.0
2-(1, l-dimethylethyl)-cyclohexanol acetate5 .0
Orange oil, cold pressed 5.0
Benzyl acetate 2.0 2.0
S Orange l~encs - 10.0
Eugenol - 1.0
Di~ t~ 9 5
Lemon oil, cold pressed - - 10.0
Total 100.0 100.0 10û.0
The rul~goillg ~e.~llc compositions are ~lmiY~cl or sprayed-onto ~typically at levels up to
about 2% by weight of the total de~r~enl composition) any of the bis-AQA su~ "1-co..l~ ;..p cle~nin~ (inrl~ in~ bl~lc~ g) compositions ~ closed herein. I,ll~roved deposition
and/or ret~?ntion of the pelrulllc or individual co~ ol~ thereof on the surface being cleaned
15 (or bl~achcd) is thus se~.ulcd.
