Note: Descriptions are shown in the official language in which they were submitted.
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PtKOXY~t~ BLEACHING COMPOSITIONS COMPRISING A FABRIC P~ult~lION AGENT
TECHNICAL FIELD
The present invention relates to aqueous ble ~~' co~-l A;-~ , compositions
sllitable for use as prel,caler and to a p,~ Al~e-~ process whereby fabric safety
and/or color safety is improved. The blc~hi~ co.~"~)os;~iQnc are preferably acidic
and comprise pcl~Aygcn bleach, plere,ably hydrogen peroxide or a source thereof,and a fabric protection agent.
BACKGROUND OF THE INVENTION
Rl3a~ g compositions have been extensively dcs~i,il,ed in laundry
applications as laundry dele~ cnls, laundry additives or even laundryy p,el,~lers.
Indeed, it is known to use such bleach-co,.~A;~ g colllposilions in laundry
plel,e~ P-~ applications to boost the removal of encrusted stains/soils and
"p,~,ble n" stains, such as grease, coffee, tea, grass, mud/clay-co.~A;..;l~g soils, which
are otherwise particularly ~lifficlllt to remove by typical m-A~hine washing. However,
a drawback associated with such bleach-co.~A;~ g compositions is that said
compositions may damage fabrics, rPs~llting in dye dAmAge and/or loss of tensilestrength of the fabric fibers, especially when used in ~ c~n~e-~l applications under
sL~c~sed corlrlitiQnc~ e.g. when applied directly onto the fabric and 1eft to act on said
fabric for prolonged periods of time before washing said fabrics, çcper;~lly when the
fabric to be treated is col~A~..;.IA~ed with metal ions such as copper, iron, .-.~nçse,
or chromium. Without being limited by theory, it is believed that the peroxygen
bleach can be ~."o.. :ble for the dye and fabric d-Amagç ~esori?t~d with these
ble- ' g co~nl~os;~iQnc It is further believed that these metal ions on the surface of
the fabrics, çsre~ lly on cellllloC;c fabrics, catalyze the dPcomrosition of peroxygen
ble ~chPs like h~dlogen peroxide. Thus, the acccl~,.atcd decc....?o~ilion of thepClo~ , bleach can result in fabric and/or dye dArnAge
When said compositiQnc are applied directly to fabrics, the di~cl e"L
co..,yon~ in said compositions diffuse or migrate, possibly at di~c.cnl rates,
through the fabric fibers. This is also true for the Pe.OA~ bleach col"ponent of
b'e ac hins~ compositionc decignPd for the PI eII ÇA ~ of fabrics.
A so!~ltiQn to the damage res~lltin~: from prtllcalillg fabrics with ble~r-hing
compositions co",p, i~ing peroxygen bleach is provided by adding certain fabric
protection agents which act to reduce fabric and/or dye ~1Am~ge These fabric
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protection agents have been found to considerab1y reduce the d~ ~e associated
with the tre~tm~nt of fabrics with peroxygen bleach-c~nl~;n.~g compositions,
especially those fabrics which are conl~l~..;n~d with metal ions. Suitable fabric
ploLt~;tion agents are chara-ilel~ed by sufflciently high stability cor..cl~.le for metal
ions, such as copper or iron, to prevent, slow, and/or ...;n;...;~e, the metal ion
catalyzed decornrosition of the peroxygen bleach. Moreover, the fabric p,oleclion
agent should have s~ffiriently high mobility to ensure that the fabric protection
agents migrates along with the peroxygen bleach as the bleach spreads or migrates
throughout the fabric fibers upon the appliC~tiQn of the bl~Lching composition onto
the fabric.
Accordinglr, the present invention solves the long-s~ g need for an
effective, dye-safe ble~chi~ composition suitable for use as a plel~eal~:r which does
not promote damage to fabrics. Moreover, the compositions of the present invention
provide ~ycpll~ont pe-rol.l,ance when used in other applications apart from laundry
p-~l,~ler application, such as in other laundry applications, as a laundry detergent or
laundry additive, or even in hard surface cle~ning appl;c~ti.7nc or in carpet clF~ning
a~ licaliolls.
BACKGROUND ART
Peroxygen bleach-co~ .;nP compositions have been extensively described in
the art For ~ EP-629,691A discloses ~mnl~ionc of nonionic surf~ct~ntc
com~rising 8 silicone compound, and as optional ingredients, hydrogen peroxide, or a
water soluble source thereo~ EP-629,690A dicclc!s~s ~mlllQ;~c of nonionic
surf~ntc comprising a terephth~l~te-based polymer, and as optional ingredients,
hydrogen peroxide, or a water soluble source thereo~ EP-209,228B discloses
cor..i-o~:~;onc Col~ g a peroxide source like hydrogen peroxide. EP-209,228B
~icrk~sec that the hydrogen peroxide-co~ n;n~ compositions may be used as pre-
s~,olle~. See also U.S. Pat. No. 4,891,147, issued Jan. 2, 1990, and U.S. Pat. No.
5,019,289, issued May 28, 1991.
SUMMARY OF THE INVENTION
The present invention enco...l~cses an aqueous composition co---p-i~--g a
peroxygen bleach, such as hydrogen peroxide or a source thereof, and a fabric
p,ole_lion agent; wherein said fabric protection agent has a mobility factor greater
than 0.7, as defined he.eil,~lel, said fabric protection agent has a stability con~l~ol of
at least log K=3 for Cu2+. Further, the minimllm cQnc~ ioll, C, of the fabric
p-ot~l;on agent, measured a_ a weight pe.~ie"l~ge of said liquid bleaç1ling
comrocitiQn, is r~lc~ fed by the following formula: {[C]*[stability co-.~ for
-
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Cu2+]} 2 2.5. Preferably, the fabric protection agents have a ratio of stabilitycon~ for copper(2+) to stability con~l~nl for c~lçi~lm(2+) of at least about 2:1.
The present invention further enco...p~c~es a process of plel,eali,lg soiled
fabrics with a liquid, aqueous composition co,.",.is;ng a peroxygen bleach and afabric protection agent having a mobility factor higher than 0.7, when measured as
defined herein, said process comprising the steps of applying said composition,
prerelably in its neat form, onto the fabric and allowing said co,l.~osiLion to remain in
contact with said fabric, plefél~bly without leaving said composition to dry on the
fabric, before said fabric is washed.
In yet another process, the aqueous composition is applied to soiled fabrics
before said fabrics are washed, ~1-~ the loss of tensile ~I,e.,~lh in said fabric is
reduced as co"",~ed to fabrics which have been treated with similar peroxygen
ble~hing compo~eitione~ but without the fabric p- ote~,lion agents of this invention.
In still yet anoll.e. process, the aqueous co...po:.;lion is applied to colored/dyed
fabrics before said fabrics are washed, whereby dye A~m~ge of said fabric is reduced
and whereby the loss of tensile strength in said fabric is reduced as con,pa-c;d to
fabrics which have been treated with similar peroxygen blF~~hins~ compositions but
without the fabric protecLion agents of this invention.
By "pl~ ,dt soiled fabrics" it is to be understood that the ~lueolle compositionis applied in its neat form onto the soiled fabric and left to act on said fabric before
said fabric is washed. Alternatively, the aqueous composition may be applied to the
fabric substrate along with enough water to wet the fabric.
In prtrt"ed emboA;~p-lre~ the present aqueous compositi~ne have a pH offrom
greater than 0 to about 6 and a viscosity of 50 cps, or greater, preferably from about
50 to about 2000 cps, at 20~C when measured with a Broo'fi~ok~ viccQ...~lFr at 50
rpm with a spindle n~3.
All p~,.c~ ~s, ratios, and plopo,lions herein are by weight, unless
otherwise ~er.;l';eA Alldocum~onts cited are h~col~JG~aled herein by r~rer~llce.
DETAILED DESCRIPTION OF THE INVENTION
The present invention F.~ço...l-~es~e an ~lueo~s composition comprising a
peroxygen bleach, such as hydrogen peroxide or a source thereof, and a fabric
protection agent. These fabric prole.;Lion agents have been found to con~iderably
reduce the d~m~e ~esoci~ted with the Llr~ nt of fabrics with peroxygen bleach-
co~ g compositione~ especi~lly those fabrics which are co..~ ted with metal
ions, such as copper, iron, chromium, and ~ gPI-ese .~I.it?/hle fabric protection
agents are characterized by sufficiently high stability col.~ for metal ions, such as
copper or iron, to prevent the metal ion catalyzed deco~ osilion of the peroxygen
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bleach. Moreover, the fabric protection agent should have s~lffiriPntly high mobility
to ensure that the fabric protection agents migrates along with the ~.e.oA~e~l bleach
as the bleach spreads or migrates throughout the fabric fibers upon the application of
the bl o e chin~ co~position onto the fabric.
The fabric ~r~.lcclion agents of this invention are ch~cle,i2cd by having a
mobility factor (defined h~,l,ci~below) higher than 0.7, p-eL.ably higher than about
0.8, more preferably higher than about 0.9. Additionally, said fabric prote~,lion
agents have a stability co~ l for copper(2+) of at least log K=3, more ~,crc,ably at
least log K=6, still more p~efclably at least log K=9, at a t~,n"~c,alLIre of 25~C and an
ionic al~ glh of 0.1. Further, said fabric protection agents preferably have a stabi1ity
CQn~ l for iron (Fe3+) of at least log K=6, more preferably at least log K=9, still
more p,~.ably at least log K=12, at a te~pci~l~lre of 25~C and an ionic allu~glll of
0.1. In more l)lcfellcd embo~ ntc, the fabric l~,oleclion agents have a ratio ofstability CQt~ l for copper(2+) to stability co~ l for cqlri~lm(2+) of at lea_t about
3:1, more pref~,.ably at 1east about 4:1. Stability conal~"ls are further defined in and
procedures for the cA~Jclill~c~ l dete~ alion of are inrl~ded in Martell, A. E.;Smith, R. M. Critical Stability Constants, Plenum Press: New York, 1974; Volume
1, and lefe.enccs cited therein. By "stability co~ '' herein is meant log K values
also decignqtecl as "log K1" as defined in Martell, cited above.
Fabric protection agents herein preferably comprise at least two moietipc
capable of ~'I'fl~l;ng or binding metal ions, such as C~bOAYIiC~ amino (plilll~y,
secol dqry, or tertiary), amido, hydroxy moietiPC and nliAIul ~s thereof. Those skilled
in the art will recognize that "carboxylic" means either carboxylic acid or the
unprotonated carboxylate. Highly plcfcilcd fabric protection agents ofthis invention
can be s~lF~lccl from the group conci~ of glycine, salicylic acid, 5-s~lfos-q-licylic
acid, 5-br4~o~licylic acid, 5-chlorosalicylic acid, aspartic acid, gll- ~~ acid,mq,lo,~ - acid, the COIICaIJOnf1;~g CO~ g~te base salts (i.e., mf~nf)Sof3i~lm g1~ e),
and "~lu,~s thereo~ Structures for thesecompounds
are:
lOH 1~l H 2N COOH
H~N~COOH ~OH
~ COOH
glydne salicylicadd asparticadd
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OH O IOH ~l OH O
SO3EI Br ~OH
''os~ J~ ~ add ~-ul.. ~ y; ~ acid~ "_yl:c acid
H2N COOH
HOOC~COOH
~COOH
glutamic acid malonic acid.
In highly prerc~.ed embotlimentc of this invention, fabric p,ole-;lion agents
which have a ratio of stability con~lA~.Ic for copper(2+) to c~ m(2~) at least about
4:1 include those agents s~l~cled from the group con~ g of glycine, salicylic acid,
5-culfos~licylic acid, 5-b~ o~licylic acid, 5-chlorosalicylic acid, glut~m:, acid,
aspartic acid, the cG,-~spol1ding conjugate base salts (i.e.""onoso~ m gl..l;....~le),
and mKtures thereo~
The especially p.~r~"ed embodiment of these fabric protection agents are those
selected from the group cQneicting of salicylic acid and its derivatives, inclu~ling 5
s~lfos~licylic acid, 5-bromosalicylic acid, 5-chlorosalicylic acid, the cG--~ ,on-iing
CO j~g~t~ base salts, and mixtures thereof.
The ...i~ -.. col-c -.~ ion of the fabric pro1eclion agents in the blc~(' ng
co~..po~ n can be c~ ted from the formula: (CXstability co~ l for Cu2+) 2
2.5, more p~efc~ly 2 5, where C is the weight percent of fabric prot~;lion agent in
the bleP.ching composition. In any case, the cor-cPntration of the fabric prote.lion
agent should be less than about 50% of the total bl3p~hir~ co-..posilion. As an
~ le, if the stability co~ for Cu2+ for a particular fabric prol~lion agent is 3,
the co~ aliun can be c~lcu1~ted by (C)(3) 2 2.5, or C is 0.83% of the total
bl~ con"~os;l.on.
In any event, a plef~ll~ range of fabric plO~,liOll agent will co-,-~"i~ from
about 0.3% to about 3%, more preferably from about 1% to about 1.5%, by weight of
the total ~le p ~hin~ composition.
The compositions accor-lh~g to the present invention are ~queo~ liquid
cl~ g con,po.;l;ons Said ~queol~s compositions should be formlll~ted in the
acidic pH, preferably at a pH of from greater than 0 to about 6 and more preferably
at a pH of from 3 to 5. Fonnl~latil~g the co~ .os;lions of the present invention in the
acidic pH range contributes to the stability of said compos;~iQnc The pH of the
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compositions of the present invention can be adjusted by using organic or inorganic
acids or bases.
By "fabric damage" herein is meant the degree of tensile strength loss of a
fabric. Tensile ~LIw~g~h loss may be measured by employing the Tensile Strength
Loss Test, as can be seen in FY~mple II heleinalle,.
Mobilit,v Factor - The mobility factor is a measure of the fabric protection
agent's ability to migrate on a c~ lose substrate and is ~ Je~ e ~lAlly dete.-l-ined in
a thin layer cl~ol..~ raphy test. The thin layer chrc"..,.lography test is cQn~lur,te~ as
follows. A sample of the fabric protection agent c~ndid~te to be ll.easured is spotted
onto a Baker-flex Cellulose F' in~ic~ting thin layer cluwllalography plate using a
capillary applicator and subseq~lently developed in an enclosed c)~ h~r using 0.001
N aqueol~c acetic acid:ethanol (50:50 mixture) as the elutant. After drying, the plates
are vic~li7ed under Wlvis light or exposure to iodine vapor. The "mobility factor"
as used herein is thus defined as the ret~ntion factor (R~, cc,.. only reco ni7ed by
those skilled in the art as the rlict~nre in which the sample moved divided by the
rlict~nce in which the solvent front moved on the thin layer .;l.r~rl.alography plate.
Thelero[e, the mobility factor, equal to the retention factor, ranges from O to 1,
with 1 being the highest mobility. The fabric protection agents of this invention
possess ~Ycçllent mobility on ce~ lose~ as measured by this mobility test. In fact, the
highly pl~f~llc;d fabric proLe.ilion agents herein have a mobility factor of 0.9 or
above.
Said thin layer ch,oulalography methods are well known in the art and are
des_l ibed for; . 'e in Touchstone, J. C. Practice of T*~n I,~yer C~ o~,.~h~t,
3rd E~*~ion, John Wiley & Sons: New York, 1992.
Peroxygen Bleach - An f sce~ l element of the colllpo~;l;o~l.c of the present
invention is p.,.~",~,~n bleach. A plert;l~cd peroxygen bleach herein is hydrogen
peroxide or a water soluble source thereof or mi~lures thereo~ Hydrogen peroxideis most pl-,rt;llcd. Indeed, the pr,sence of peroxygen bleach, pref.,.ably hydrogen
peroxide, provides strong c1e.l-~;ng benefits which are particularly noticeable in
laundry applic~tinnc As used herein, a hydrogen peroxide source refers to any
co...l-o~ which produces hydrogen peroxide when said compound is in contact
with water.
Suitable water-soluble sources of hydrogen peroxide for use herein include
sodium carbonate peroxyhydrate or equivalent pel.,all,ol1ale salts, persilicate,pe.borates, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-
hydrate), sodium pyrophosphate pero~yllydrate, urea perox~h~dl~e, sodium
peroxide, and mixtures thereof. Alternative peroxygen sources include persulfates
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such as monopersulfate, peroxyacids such as di~)erOArdOd~Pc~n~iiQic acid (DPDA),m~gnesillm perphth~l~tic acid, perben_oic and alkylp~,l,e.~oic acids, and mixtures
thereof.
An "effective amount" of a peroxygen bleach is any amount capable of
measurably improving soil/stain removal from the soiled fabric substrate c~."",ared to
a pero~y~en bleach-free composition when the soiled sL-bsl,ale is washed by the
conC~mer in the plesence of alkali. Typically, the compositions of the present
invention CGIll~J~i3e from 0.5% to 20% by weight of the total composition of said
peroxygen bleach, preferably from 2% to 15% and most p,tre, al~ly from 1% to 6%.Optional Bleach Activators - The peroxygen-co~ h~ , co",pos;lions herein
may optionally, but preferably, further comprise a bleach activator. By bleach
activator, it is meant herein a compound which reacts with hydrogen peroxide to
form a peracid. The peracid thus formed co~ctihltes the activated bleach.
Particularly plerelled is acetyl triethyl citrate. Said bleach activators, if present, will
typically CC~ JliSe from about 0.5% to about 20%, pr~fe,ably from 2% to 10%, most
plèrel~.bly from 3% to 7%, by weight of the total cG...ro~:l;on
Bleach activators suitable herein are any known activators typified by NOBS
(nonanoyl oxybçn7Pne~ fonate), TAED (tetraacetylethyl~ne~ .e), or ATC
(acetyl triethyl citrate). Numerous other bleach activators are known. See for
e.~a",ple activators referenced in U.S. Patent 4,915,854, issued April 10, 1990 to
Mao et al, and U.S. Patent 4,412,934. See also U.S. 4,634,551 for other typical
convention~l bleach activators. Also known are amido-derived bleach activators of
the formulae: RlN(R5)C(O)R2C(O)L or RlC(O)N(R5)R2C(O)L wherein Rl is an
alkyl group CGn~ g from about 6 to about 12 carbon atoms, R2 is an alkylene
co~ B from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl
c~ ;..;ng from about 1 to about 10 carbon atoms, and L is any suitable leaving
group. Further illustration of bleach activators of the above formulae include (6-oct-
zm~m;dQcaproyl)-ox~b ~ n~, ~lfonate, (6-no~ ;docaproyl)~,Arl,~n,~ ne, ~lfonate,
(6-de~ idocaproyl)o~ .7~ 1fonate, and mixtures thereof as desc,;l,ed in
U.S. Patent 4,634,551. Another class of bleach activators CGIll~l;3eS the b~ s 7;n-
type activators ~ osed by Hodge et al in U.S. Patent 4,966,723, issued October 30,
1990. Still another class of bleach activators inrl~des acyl lactam activators such as
substituted and unsubstituted benzoyl caprol~ct~m, t-butyl-benzoylcaprol~ct~m, n-
octanoyl caprol~ct~m, 3,5,5-trimethylhexanoyl caprol-~t~m, nonanoyl caprolactam,decdllOyl capro~ m, l~nrlecPnoyl caprolart~m octanoyl valerolact~m, decanoyl
valero~ m ImdecenQyl valerol~ct~m, nonanorl valero1actam, 3,5,5-
~liln~ lylh~ .~n~yl valerol;lct~m t-butyl-benzoylvalerol~cPm and mixtures thereof.
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Prer~. r~,d bleach activators useful herein include those sele~;led from the
group CQn~;SI;~ of acetyl triethyl citrate, n-octanoyl caprolactam, 3,5,~-
trimethylhexanoyl caprol~ctAm, nonanoyl caprolactam, decanoyl caprolAct~m~ n-
octanoyl valerolactam, 3,5,5-1,i,nc;l}lylhexanoyl valerolactam, nonanoyl valerol~ctAm,
decanoyl valerolactam, llillùbe~oyl caprolactam, til- oben~;oyl valerol~,t~m andmixtures thereo~ Particularly plerell~,d are the bleach activators which are liquid or
oil at room ttlllpe~aLure. I:,.~.lples of liquid bleach activators are acetyl triethyl
citrate, n-octanoyl caprolact~m 3,5,5-1~ilnelllylk~ uyl caprolactAm, nonanoyl
C8PIO~ A~.., decano~l capro~ n~ and IlliAl~lleS thereo~ The present co".posilions
can optionally cG",~,ise aryl ben~oAl~s~ such as phenyl bPn7o~te.
~ lell~al.llenl Process - Although plerelled application of the compositions
described herein is laundry pl~,lleA~ lt the compositions acco,-ling to the present
invention may also be used as a laundry d~,lel~elll or as a laundry delel~ booster
and as a hol-cphold cleaner in the bathroom or in the kit~.h~n, for the ~1e~ning of
dishes or for the rlP~nin~ of carpets.
Said composition may remain in contact with the fabric, typically for a period
of 1 minute to 24 hours, preferably 1 minute to 1 hour, and more preferably 5
mimlteS to 30 minlltec, or so as to avoid drying of the composition on the fabric.
Optionally, when the fabric is soiled with encrusted stains/soils which otherwise
would be relatively difficult to remove, the compositions according to the present
invention may be rubbed and/or brushed, for cA~---ple, by means of a sponge or abrush or simply by rubbing two pieces of fabric each against the other.
By ''~.~I,mgU it is to be understood herein to simply rinse the fabrics with
water, or the fabrics may be washed with conventional compositions com~ g at
least one surface active agent, this by the means of a washing mA~hine or simply by
hand.
By "in its neat form" it is to be understood that the compositions described
herein are applied onto the fabrics to be pre-treated without undergoing any dilution,
i.e. they are applied in the form described herein.
Qther ConvçntiorlAl In~ledi~ s for Cleaning ColllposlLions - The ~lueQI-c
b,'e 8~ compositionc herein typically will also comprise other optional
conventional ingredients to improve or modify pe.r.""-ance. Typical, non-limiting
of such ingredie.lls are ~~icclosed helein~ler for the convenience of the
formulator.
Organic Stabilizers - The compositions herein may also optionally contain
organic ;"~hil;~ for improving the chemical stability of the composition, provided
that such materials are co...p ~ le or suitably formulAte(i Organic st~hili7.ors can be
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s~leclecl from the following group: monophenols such as 2,6-di-tert-butylphenol or
2,6-di-tert-butyl4-methylphenol; ~liph~nol~ such as 2,2'-methylenebis(4-methyl-6-tert-
butylphenol) or 4,4'-methylenebis(2,6-di-tert-butylphenol); polyphenols such as 1,3,5-
trimethyl-2,4,6-tris(3',5'-di-tert-butyl~-hydroxybenzyl)ben7ene; hydroq~inonçs such as
2,5-di-tert-amylhydroqninorle or tert-butylhydroquinone; aromatic amines such as N-
phenyl-N'-(1,3-dimethylbutyl)-p-phenylçn~ c or N-phenyl~c-napthylamine;
dihyd,o~ui.lolines such as 2~2~4-l~h~ l.yl-l~2-dihydro-~-int~line; ethane-l-hydroxy-
iphosl)ho,~te and other known ph~sphonRtes (see, for eA~IFle, U.S. Patents3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137), and mixtures thereof.
Organic stabilizers are typically used in the present compositions at levels from
0.01% to 5.0%, more pler~lably from 0.1% to 0.5%.
The peroxygen bleach-co..~ ing compositions according to the present
invention may further CGIllpliSe from 0.5% to 5%, pl~,f~.i.bly from 2% to 4% by
weight of the total composition of an alcohol accoldhlg to the formula HO - CR'Rn -
OH, wh~rei~ R' and R" are inr~ep~n~lently H or a C2-C10 hydrocarbon chain and/orcycle. F~-er~ d alcohol accordil~g to that formula is prul)An~iol.
In~ nic St~Rbili7ers - E~lllples on inorganic stRbili~e~s include sodium
stRnnRte and various alkali metal phosphates such as the well-known sodium
tripolyphos~h~.les, sodium ~ ophosphate and sodium ollhophosphRte.
Detersive SurfR~.t~ntc --SurfRctRnte are useful herein for their usual ~ ,g
power and may be inrl~lded in pl-;r~:lled embo-l;...,.~ls of the instant compocitionC at
the usual detergent-useful levels. Generally, surfRctRntc will Ccil..~J-ise from about
0.1% to about 50%, preferably from about 1% to about 30%, more prer~.ably from
about 5% to about 25%, by weight of the liquid b'c~ ' 1,3 compositionC herein.
No~ g c . I-s of surfRctRntc useful herein include the convçntionRI
Cll Clg alkyll~ sulronales (HLAS") and primary, bl~clled-chain and random
Clo-C20 alkyl sulfates (nASN); the Clo-Clg secondaly alkyl sulfates of the formula
CH3(CH2)X(CHOSO3 M+)CH3 and CH3(CH2)~,(CHOS03 M+)CH2CH3 where x
and (y + 1) are inlege.~ of at least about 7, preferably at least about 9, and M is a
water-sohJl.il;,;ng cation, especially so~ m; unsaturated sulfates such as oleylsulfate; the Clo-Clg alkyl alkoxy sulfates (HAEXS") especi~lly those Whe[~,;ll X iS
from 1 to about 7; C l o-C l g alkyl alkoxy carboxylates (espe~ y the EO l -S
ethox~c~l,uAylates); the Clo-Clg glycerol ethers; the Clo-C18 alkyl polyglycosides
and their coll~ o~d~ s-llfRted polyglycosides; and C12-C18 alpha-sulrollaled fatty
acid esters. Detersive surfiRctRntc may be mixed in varying plul)ollions for improved
sLIrà.,l~l~ as is well-known in the art. Also optionally in~ l.ied in the compositions
are conventiorlRI nonionic and amphoteric surf~ct~nts such a_ the C12-Clg alkyl
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ethoxylates (~AEH) inr~ iing the so-called narrow peaked alkyl ethv~lates and C6-
C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxylate/
propoxylates), C12-Clg betaines and sulrobelah,es (~s~ rs~ Clo-Clg amine
oxides, and the like, can also be included in the cle~ning compositions, The Clo-Clg
N-alkyl polyhydroxy fatty acid amides can also be used. Typical ~ !e~ include
the C12-Clg N-methyl~luc~mid~e See WO 9,206,154. Other sugar-derived
Su~r~c~ include the N-alkoxy polyhydroxy fatty acid amides, such as Clo-Clg N-
(3-metho,.~ v~,~l) gh~r-~mide The N-propyl through N-hexyl C12-Clg gl-Jc~mi~es
can be used for low s~ cing Clo-C20 conventional soaps may also be employed. If
high sudsing is desired, the branched-chain Clo-C16 soaps may be used. Mixtures of
anionic and nonionic surf~ct~rlte are especially useful.
Builders - Detergent builders can optionally be inr.luded in the compositions
herein to assist in controlling mineral hald.less. Inorganic as well as organic builders
can be used. Builders are t,ypically used in fabric laundering co,--pos;lions to assist in
the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically com~).;se at least about 1% builder. High pe~rullllancc compositions
typically colll~l;se from about 10% to about 80%, more typically from about 15% to
about 50% by weight, of the detergent builder. Lower or higher levels of builder,
however, are not PYclu~ied
Organic detergent builders suitable for the purposes of the present invention
inrludf~., but are not restricted to, a wide variety of pol~,~,a-l,uAylate compounds. As
used herein, NpolycarboxylateH refers to compounds having a plurality of carboxylate
groups, plefcl.~bly at least 3 carboxylates. Polyca-l,v~ylate builder can generally be
added to the composition in acid forrn, but can also be added in the forrn of a
neutralized salt or "overbased". When utilized in salt form, alkali metals, such as
sodillm poPceillm and lithium, or alkanolammonium salts are plefell~d.
Tnc~ led among the polycarboxylate builders are a variety of ca~egc,-;cs of
useful materials. One ;l-"~o,lant category of polycarboxylate builders ~.~ro~ cses
the ether polycarboxylates, inrlu~1ing oXyrlieuccin~te~ as rlier~osed in Berg, U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830,
issued Janualy 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include
cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
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Other useful dt;le~ ncy builders include the ether hydroxypolycarboxylates,
copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy
be.~ene-2,4,6-trie llfonic acid, and carboxymethyloxysucçinic acid, the various alkali
metal, a~,.nlol ium and s~lbstitutçd ammonium salts of polyacetic acids such as
nitrilotriacetic acid, as well as pol~call,uA~lates such as mellitic acid, su-~ ~e acid,
oxyflicucçinic acid, polymaleic acid, be~.~e--e 1,3,5-tricalbuAylic acid,
carboxymethyloxysuccin;G acid, and soluble salts thereûf.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium
salt), are poly-,a.l,oAylate builders of particular i~llpGll~ce due to their availability
from renewable resources and their biodegradability. oxy~licuc~ es are also
especially useful in such compositions and co~ ;onc
Also suitable in the detergent compositions of the present invention are the 3,3-
dicarboxy-4-oxa-1,6-h-,~ edio~tes and the related compounds ~iisc~osed in U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful s~ccin;C acid builders
include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. Specific
examples of sucrin~te builders include: laurylc~crin~te~ y~i~lyi~le~in:~t~
palmitylc-~cçin~te, 2-dodecenylc~lcçin~te (p.~ ,d), 2-p~nt~decenylcucçin~tç~ andthe like. Laurylc~lc~ es are the pl~ d builders of this group, and are des~-i1.ed
in European Patent Applic~tion 86200690.5/0,200,263, published November 5,
1986.
Other suitable pol~,calloAylates are disclosed in U.S. Patent 4,144,226,
Cn~t~-hfi~ld et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued
March 7, 1967. See also U.S. Patent 3,723,322.
Fatty acids, e.g., C12-Clg monocarboxylic acids, can also be i Ico.~,o.;~led into
the CO...I~O~ C alone, or in con-l,i~-~lion with the alor~,~aid builders, especially
citrate and/or the s~ccin~te builders, to provide ~dditiQn~l builder activity. Such use
of fatty acids will generally result in a diminutior~ of sudsing in laundry co,l-positions,
which may need to be taken into ~cco~nt by the formulator.
Where pho~hû- .~s-based builders can be used, and ecreci~lly in hand-
laundering operations, the various alkali metal phosphates such as the well-known
sodium tripolyphosphates, sodium pyrophosph~te and sodium orthopho:,l h~l~ can be
used. phosl~ho~ e builders such as ethane-l-hydroxy-l,l-~iirhos~Jhon~e and otherknown phosphon~tes (see, for example, U.S. Patents 3,159,581; 3,213,030;
3,422,021; 3,400,148 and 3,422,137) can also be used though such materials are
more cG~ only used in a low-level mode as ch~ or stabilizers.
Llol~;~ic or P-co.~ -h-g detergent builders incl~dç, but are not limited to, thealkali metal, ~Illllon..lm and alkanolammonium salts of polyphosph~tes (exemplified
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by the tripolyphosph~tçc, pyrophosphates, and glassy polymeric meta-phosphales),pho~honales~ phytic acid, eilir ~tPS~ carbonates (in~ din~ bicarbonates and
sesqui.,~l,onales), s~lf~t~c and ~ minosili~tes
ChPl~tin~ Agents - The compositions herein may also optionally contain a
tr~ncition-metal selective seq~le,~ or "chPl~tin~ agents", e.g., iron and/or copper
and/or m~ng~nçse chPl~ting agents, provided that such materials are con"~_lil>lc or
suitably forrn--l~fe~ Chel~ting agents suitable for use herein can be sPlected from the
group cor~cicting of ~minoc~rboxylates, phosrhor~~tçs (çcpeci~lly the
~",no~hos~.hon~lts), polyfunctionally-substihlted aromatic rh~l~tin~ agents, andmixtures thereof. Without intçnr1ing 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,
copper and m~ng~n~ce ions from washing solutionc by formation of soluble "hf~l5.l~c,
other be~ tc include inorg~uuc film prevention or scale inh;~ ition. Conul-~;lcial
~~.hPl~ti~ agents for use herein include the DEQUEST(~ series, and çh~l~ntc fromMon~n~o, DuPont, and Nalco, Inc.
Aminocarboxylates useful as optional ~ ting agents are further illustrated by
ethylen~ n~inetetraçet~t~c N-hydroxyethylethylPnP~ . ;Acet~tec
nitrilol,;~cet~lcs, ethyl~nerii~minp tel,~prop,ionates,
triethylènelell ~A~ pk ~ ~et~tçc diethylenel, ;~ epçnt~cet~tPc and
eth~nol~iElycines, alkali metal, ammonium and substituted ammonium salts thereof.
In general, chelant mixtures may be used for a cor,.bh~ation of functions, such as
mll1tirle tr~ncition-metal control, long-term product stabilization, and/or control of
pl~ ted tr5-ncition metal oxides and/or hydroxides.
polyflln~tiQn~lly-sllbstil-~lted aromatic çhPl~ting agents are also useful in the
co-..po:,ilions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et
al. P~er~,.led compounds of this type in acid form are dihydlo~cy~lielllfob~P~ f c such
as 1,2-dihydroxy-3,5-disul~b~n7ene
A highly ~n~relled biodegradable ch~l~tor for use herein is ethy~ e~ e
dicucçin~te (nEDDS"), esreci~1ly (but not limited to) the [S,S] isomer as dese,ibed in
U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. The trisodium
salt is prêfe~cl though other forms, such as m~r~nPcillm salts, may also be useful.
Another preçel ~ ed chelalol for use herein is of the formula:
RlR2R3
CX~H 5R4 ~ IR2R~
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wherein Rl, R2, R3, and R4 are indepe~ P~tly selected from the group con~ieting of
-H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO2, -C(O)R', and -SO2R"; wherein R' is
sPIected from the group cor.~:c~ P. of-H, -OH, alkyl, alkoxy, aryl, and aryloxy; R" is
s~le~ltd from the group cor~ ting of alkyl, alkoxy, aryl, and aryloxy; and Rs, R6,
R7, and R8 are indel-el-dr..ll~ selected from the group cor cicting of -H and alkyl.
A,. i.,ophosphonates are also suitable for use as c~ agents in the
cc"..~,osilions of the invention when at least low 1evels of total phosphorus are
pe~ led in detergent composition~ and include the ethylen-J;~ el~:t~ ~kis
(methylPnephosl-ho~ Ps) and the diethylenel~;A.,,:-~p~
(methylPnephQsphonates). Preferably, these aminophosphonates do not contain alkyl
or alkenyl groups with more than about 6 carbon atoms.
If ~-tili7e~1, .'1,~1,.~;..13 agents or tr~ncitiorl-metal-selective seque~tia,.ls will
preferably COIlll~liSe from about 0.001% to about 10%, more preferably from about
0.05% to about 1% by weight of the compositions herein.
Enzyrnes - Enzymes can be included in the instant compositions for a wide
variety of fabric laundering or other cle~ning purposes, in~lu~i~ removal of protein-
based, carbohydrate-based, or triglyceride-based stains, for ~y~mrle~ and for the
prevention of refugee dye t~ sre" and for fabric restoration. The el~yn.es to beincorporated include proteases, amylases, lipases, c~llul~cps~ and peroxi~cec, as well
as mixtures thereof. Other types of enzymes may also be in~ luded They may be ofany sllit~hle origin, such as veget~hle, animal, bacterial, fungal and yeast origin.
However, their choice is governed by several factors such as pH-activity and/or
stability optima, therrnostability, stability versus active d~Le.~ ls, builders, etc.. In
this respect bacterial or fungal enzymes are plerelred~ such as bacterial arnylases and
p~ lcases~ and fungal celllll~C~s The enzymes useful herein may optionally be coated
for protection in the flqueollc formulation.
Enzymes are normally incc"~,o,~.ted at levels sufficient to provide up to about 5
mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per
~am of the composition. Stated otherwise, the compositions herein will typicallycc""~";~ from about 0.001% to about 5%, plere-~bly 0.01%-1% by weight of a
co..... -~ c;al enyme p. epal ~lion. Protease enzymes are usually present in such
co,.,.. ~,.cial pr~a,~lions at levels sufficient to provide from 0.005 to 0.1 Anson units
(AU) of activity per gram of comrosition
.Sllit~bl~ ~".a" "le~ of proteases are the subtilisins which are obt~ined from
particular strains of B. subtilis and B. Iich~niJ~r~,.is. Another suitable protease is
ob~ d from a strain of ~ , having maximum activity throughout the pH range
of 8-12, dcvelol)ed and sold by Novo Industries A/S as ESPERASE~). The
-
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plepa-,lLion of this enzyme and analogous enzymes is described in British PatentSpecific~tiQn No. 1,243,784 of Novo. Proteolytic enzyrnes suitable for removing
protein-based stains that are co.. ç~,ially available include those sold under the
tr~d~Pn~mP,s ALCALASE~ and SAVINASE~ by Novo Industries A/S (Dc.",la,k)
and MAXATASE/~ by International Bio-S~ el;r,s7 Inc. (The N~;lh~ ds). Other
p,~ol~ases include Protease A (see European Patent Application 130,756, published
January 9, 1985) and Protease B (see European Patent ~rplic~tion Serial No.
87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et
al, published January 9, 1985).
An especially p,~,ft;"~;d protease, referred to as "P~oltase D" is a carbonyl
hydrolase variant having an amino acid seq~lPnce not found in nature, which is
derived from a precursor carbonyl hydrolase by s~lbctih~ting a di~c,_nl arnino acid for
a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent
to position +76 in cc,...l-inAI;on with one or more arnino acid residue positions
equivalent to those selected from the group consisting of+99, +101, +103, +107 and
+123 in R~ ,c amyloliquefaciens subtilisin as described in the patent appli~tionc
of A. Baeck C.K. Ghosh, P.P. Greycar, R.R. Bott and L.J. Wilson, entitled
"Protease-Con~ g Cleaning Compositions" having U.S. Serial No. 08/136,797
(P&G Case 5040), and "Bleaching Co"~posilions Comprising Plotc;ase En~yrnes"
having U.S. Serial No. 08/136,626.
Arnylases incl~de, for CAalllp10, a-amylases described in British Patent
Spe~ifi~tiorl No. 1,296,839 (Novo), RAPIDASE~), International Bio-SynthPticc,
Inc. and TERMAMYLtg), Novo Industries.
C~ç~ ePs usable in the present invention include both bacle, ial or fungal
CPl~ cPs P~f~ bly, they will have a pH optimum of b,_l~n S and 9.5. S~it~hle
cPll-ll~ces are d;~losed in U.S. Patent 4,43S,307, Barbesgoard et al, issued March 6,
1984, which r~ oses fungal cel~ ce produced from HV~ k~ insolens and
H~ strain DSM1800 or a cP~ ce 212-producing fungus belonging to the
genus A~c,,v. ,~s, and cellul~CP extracted from the hepato~anc,_as of a marine
moll~Q~ (D~lnbe~ AtJric~ la Solander). Suitable ce~ ces are also dicelnsed in GB-
A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME(~) (Novo) is
especi~lly useful.
!Suits~ lipase enymes for detergent use include those produced by
microor~ of the Psetr~omQnas group, such as Ps.~ onas s~2~tzeri ATCC
19.154, as tlis~osed in British Patent 1,372,034. See also lipases in J~pan~se Patent
~p~ cal;o" 53,20487, laid open to public inspection on February 24, 1978. This
lipase is available from Amano Pharm~ce~tic~l Co. Ltd., Nagoya, Japan, under the
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trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other
cQ.. ~lcial lipases include Amano-CES, lipases ex Ch~ bnct~r vi.~Qs~n, e.g.
Ch,, . ~b~rt~r vi.~as~>n var. Iipolyticum NRRLB 3673, cc,~ c;ally available fromToyo Jozo Co., Tagata, Japan; and further Chromobacter vi.~os~n lipases from U.S.
Ri~c1.r....:c~1 Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
P~ ' . ,..2s glaclioli. The LIPOLASE~ enzyme derived from H2-mi~
la~uginosa and co..~ c;ally available from Novo (see also EPO 341,947) is a
p-crtlled lipase for use herein.
Peroxidase enzymes can be used in co...hi~ on with oxygen sources, e.g.,
percarbonate, pc.l,or~le, persulfate, hydrogen peroxide, etc. They are used for
"solution ble?,chi~," i.e. to prevent transfer of dyes or pi~nentc removed from
al~,s during wash operations to other substrates in the wash solution.
Per~da~ enzymes are known in the art, and includf~J for ~ , horseradish
peroYi~l~ce~ lignin~c~:, and haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase-col.l~ g dc~el~clll compositions are disclosed, for e,A~n?le, in PCT
Intcll.~l;Ql-~1 Application WO 89/099813, published October 19, 1989, by O. Kirk,
acci ned to Novo Industries A/S.
A wide range of enzyme materials and means for their inco,~o.~lion into
synthetic d~,Le,~5cnl compositions are also disclosed in U.S. Patent 3,553,139, issued
January S, 1971 to McCarty et al. En_ymes are further rli~tlosed in U.S. Patent
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes,
issued March 26, 1985. Enzyme materials useful for liquid detergent formulations,
and their illcOl~JulaliOll into such forrn~ tiQns~ are disclosed in U.S. Patent
4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in dch~gc~lls can be
st~hili7f~d by various techniques. Enzyme st~hili7~tion ta ' ques are dicclnsed and
~ -f ..~ d in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and
European Patent Appli~ ~tior Public~tion No. 0 199 405, Application No.
86200586.5, p~h!ished October 29, 1986, Venegas. En_yme sl~;li~liGn systems
are also de_.il,ed, for e,. ple, in U.S. Patent 3,519,570.
Polymeric Soil Release Agent - Any polymeric soil release agent known to
those skilled in the art can optionally be employed in the comros;tions and processes
of this invention. Polymeric soil release agents are characterized by having both
l.~d~philic s~ ".~ c, to hydrophilize the surface of hydrophobic fibers, such aspolyester and nylon, and hydrophobic se~msntc, to deposit upon hydrophobic fibers
and remain adhered thereto through comrletion of washing and rinsing cycles and,thus, serve as an anchor for the hydrophilic se~...f ~lC This can enable stains
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occurring subsequent to hei~ f-~l with the soil release agent to be more easily
c1eaned in later washing procedures
The polymeric soil release agents useful herein ecpe~ y include those soil
release agents having: (a) one or more nonionic hydrophile componenLs con~ictin
r55f;~ 11y of(i) polyoxyethylene se~ nlC with a degree of poly...e.i~dlion of at least
2, or (ii) uAyl~ upylene or polyu~p~u~,ylene sc~ with a degree of
poly~ ion offrom 2 to 10, wherein said hydrophile se~.n~ .l does not e~-cQ~..p~cc
any oxypropylene unit unless it is bonded to ~dj~c~f nt mnieti~c at each end by ether
l G ~ s, or (iii) a mixture of oxyalkylene units co---p- ;s;--~ y~LL~lene and from 1 to
about 30 oxypropylene units wherein said mixture cG--lains a s~fficient arnount of
oxyethylene units such that the hydrophile component has hydrophilicity great
enough to in.,l ~ase the hydrophilicity of convçntion~l polyester synthetic fiber
surfaces upon deposit of the soil release agent on such surface, said hydrophilesep.~ lc ~rérc.~bly COUI~,l;S;llg at least about 25% o"~ lene units and more
~lerel~bly~ especially for such COIll~Ollelll.7 having about 20 to 30 oxypropylene units,
at least about 50% oxyethylene units; or (b) one or more l.~.lrophobe co---pûne-~l~7
comprising (i) C3 oxyalkylene terephth~l~te se~rnPntc, wh~le;l~7 if said hydrophobe
CQ~pO~ le also co---p-ise oxyethylene terephth~l~te~ the ratio of oxyethylene
te.e~ te:C3 oxyalkylene terephth~l~te units is about 2:1 or lower, (ii) C4-C6alkylene or oxy C4-C6 alkylene segm~ntc or mixtures therein, (iii) poly (vinyl ester)
Se~ .fS,plerel~ly polyvinyl acetate), having a degree of pol~,..e.~Lion of at least
2, or (iv) Cl-C4 alkyl ether or C4 hydroxyalkyl ether ~I.h~ ontc~ or mixtures
therein7 wll~.ein said substitllents are present in the form of Cl-C4 alkyl ether or C4
LydluAyalkyl ether c~l1ulQse derivatives, or rnixtures therein7 and such c~ losederivatives are~ ~...phirl.ilic, wL.,Ieby they have a s~fficient level of Cl-C4 allyl ether
and/or C4 I.~d.uA~lkyl ether units to deposit upon conventional polyester synthetic
fiber surfaces and retain a suffi~ient level of hydroxyls, once adhered to such
convention~ elic fiber surface, to inclease fiber surface hydrophilicity, or a
co..-l~;n~l;o-- of(a) and (b).
Typically, the pol~oA~etlly1ene s~. . .~ t c of (a)(i) ~vill have a degree of
pol~--.e.~alion of from about 1 to about 200, ~lthough higher levels can be used,
pre~.~bly from 3 to about 150, more preferably from 6 to about 100. Suitable oxyC4-C6 alkylene ll~rd~ophobe se~ ne nle include, but are not limited to, end-caps of
polymeric soil release agents such as MO3 S(CH2)nOCH2CH2O-, where M is
sodium and n is an integer ~om 4-6, as t~ieclosed in U.S Patent 4,721,580, issued
January 26, 1988 to Goce~lint
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Polymeric soil release agents useful in the present invention also include
cell--losic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks
of ethylene terephthAl~te or propylene terephthAl~te with polyethylene oxide or
polypropylene oxide terephthAlAte, and the like. Such agents are co.. ercially
available and include hyd- o~clhers of cellulose such as METHOCEL (Dow).
C~ll--lo~;c soil release agents for use herein also include those sP~le~;~cd from the
group con!~:c~ g of Cl-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent
4,000,093, issued Dece-..her 28, 1976 to Nicol, et al.
Soil release agents cl-a,a~;Lt.~Gd by poly(vinyl ester) hydrophobe se~ e~
include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, prGre.~bly
poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene
oxide backbonGs. See European Patent Application 0 219 048, published April 22,
1987 by Kud, et al. Co--,n-c-~,;ally available soil release agents of this kind include
the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF
(West C;~
One type of prGre ~ed soil release agent is a copolymer having random blocks
of ethylene terephth~lAte and polyethylene oxide (PEO) te,e~ l.Al~te. The molecular
weight of this polymeric soil release agent is in the range of from about 25,000 to
about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S.
Patent 3,893,929 to R~c~dur issued July 8, 1975.
Another p~,rG..~,d polymeric soil release agent is a polyester with repeat unitsof ethylene te.~ hAl~te units conlains 10-15% by weight of ethylene terephthAl~te
units to~ with 90-80% by weight of polyoxyethylene te,~pkll.~lAte units, derivedfrom â polyoA~_Il,ylene glycol of average m~le ~l~r weight 300-5,000. FY~mrl~ ofthis polymer include the co.. ~.-,;ally available material ZELCON 5126 (fromDupont) and MILEASE T (from ICI). See âlsO U.S. Patent 4,702,857, issued
October 27, 1987 to Gosselink
Another pl~r~,.-t:d polymeric soil release agent is a sulr~llaltd product of a
SU~ ;AIIY linear ester oli~omer cG--.p,ised of an oligo,..~.ic ester backbone oftt;l~klh~loyl and oxyalkyleneoxy repeat units and terminal n.a~ - covalently
~tf~ched to the backbone. These soil release agents are desc,ibed fully in U.S. Patent
4,968,4Sl, issued November 6, 1990 to J.J. Scheibel and E.P. Goss~lin~ Other
s ~- b!~ polymeric soil release agents include the ttrc~,hll.~l~te polyesters of U.S.
Patent 4,711,730, issued Decemher 8, 1987 to Goec~link et al, the anionic end-
capped oligo"~.ic esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosc~lin~ and the block polyester oligomeric compounds of U.S. Patent 4,702,857,issued October 27, 1987 to Goss~olink
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Plcrc~ed polyrneric soil release agents also include the soil release agents of
U.S. Patent 4,877,896, issued October 31, 1989 to ~1~1On~dQ et al, which dicclosçc
anionic, çsperi~lly sulfoaroyl, end-capped terephth~iQte esters.
Still another plcre--ed soil release agent is an oligomer with repeat units of
teltpl.Ll-aloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-
propylene units. The repeat units form the backbone of the oli~Qmer and are
pl~fc~ably t~ ed with .nod;l~ed isethionate end-caps. A particularly l~lerc-~cd
soil release agent of this type comprises about one s~llroicophthaloyl unit, 5
ttrel-hll~loyl units, oxyethyleneu~y and oxy-1,2-propyleneo,~r units in a ratio offrom
about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-h~d~o~ycllloxy)-
clh~ne~..-lfonate. Said soil release agent also cou~ iscs from about 0.5% to about
20%, by weight of the oligomer, of a crystalline-reducinf~ stabilizer, preferably
selected from the group con~-;c~ of xylene s~lfon~tr, cumene snlfon~te~ toluene
sulfonate, and mixtures thereof. See U.S. Pat. No. 5,415,807, issued May 16, 1995,
to Go,ccçlin~ et al.
If utili7e~l~ soil release agents will generally cGm~rise from about 0.01% to
about 10.0%, by weight, of the detergent compositions herein, typically from about
0.1% to about 5%, p~crc-ably from about 0.2% to about 3.0%.
Other Ingredients - Detersive ingredients or adjuncts optionally included in theins~nt compositions can include one or more materials for ascicting or enh~n~-in~
cieaning pc,ro..,lance, I-ç~ of the substrate to be cl~ne~l or dçsis:~ned toimprove the ~esthetic s of the compositions. Such materials are further illustrated in
U.S. Pat. No. 3,936,537, Baskerville et al. ~ lnctc which can also be inrll-ded in
compositiQnc of the present invention, in their conventional art-established levels for
use (generally from 0% to about 20% of the detergent ingredients, plcrc-ably from
about 0.5% to about 10%), include other active ingredients such as dis~e-:,d--
~polymers from BASF Corp. or Rohm & Haas; anti-tarnish and/or anti-corrosion
agents, dyes, fillers, optical brightenPrs, germi~ides~ h~d-vt~vpes, enzyme stabilizing
agents, perfumes, sol~bili~i~ agents, clay soil removaVanti-redeposition agents,carriers, p,occ,~ aids, pigm~ntc solvents, fabric son~ , static control agents,
etc.
Dye Transfer Inhibiling Agents - The compositions of the present invention
may also include one or more materials effective for inhibiting the t~ansrer of dyes
from one dyed surface to another during the rl.o~nin~ process. Generally, such dye
hah~rcr u~ ilh-g agents include polyvinyl pyrrolidone polymers, polyamine N-oxide
polymers, copolymers of N-vinylpyrrolidone and N-vinylimirl~7Ole, m~nE~n~se
phthalocyanine, peroxi-i~ces~ and mixtures thereof. If used, these agents typically
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comprise from about 0.01% to about 10% by weight of the composition, preferably
from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More speçifi~ y~ the polyamine N-oxide polymers plere~léd for use herein
contain units having the following structural formula: R-AX-P; wLc.eill P is a
polymerizable unit to which an N~O group can be ~tt?chPd or the N~O group can
form part of the polymerizable unit or the N~O group can be ~ttachPd to both units;
A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1;
and R is aliphatic, ethoxylated ~liph~ti~c aromatics, heterocyclic or alicyclic groups
or any colll~illalion thereof to which the nitrogen of the N~0 group can be ~ttached
or the N~O group is part of these groups. Pl èrel I ed polyamine N-oxides are those
wheléin R is a heterocyclic group such as pyridine, pyrrole, i..~ cle pyrrolidine,
piperidine and derivatives thereof.
The N~O group can be repres~ ed by the following general structures:
O O
I)x ~ R2~y; =N--~Rl)x
~3)z
wherein Rl, R2, R3 are ~liph~tic~ aromatic, heterocyclic or alicyclic groups or
colllb;~ ;ons lll~or~ x, y and z are 0 or 1; and the nitrogen of the N~O group can
be ~tt~hed or form part of any of the aforem~ntioned groups. The amine oxide unit
of the polyamine N-oxides has a pKa <10, preferably pKa <7, more ~b~erelled pKa
<6.
Any polymer backbone can be used as long as the arnine oxide polymer
formed is water-soluble and has dye llallsrel inhibiting properties. F.~ les of
Y.lit~bl~ polymeric bael~olles are polyvinyls, polyalkylenes, pol~e~lel:i, poly~llle.~,
pol~alll,de, polyimides, polyacrylates and mixtures thereo~ These polymers include
random or block copolymers where one ,..onon~ type is an amine N-oxide and the
other ...~n~sl... r type is an N-oxide. The amine N-oxide polymers typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropliale copolyllleli~lion or by an appl~,pliate degree of N-oxi~tion The
e polyall~ne oxides can be oblah~ed in almost any degree of polylneli~alion Typically,
the average ms)lec~ r weight is within the range of 500 to 1,000,000; more plefelled
1,000 to 500,000; most pl~,fe.l~d 5,000 to 100,000. This prefélled class of materials
can be l~,f~.led to as "PVNO". The most plerélled polyamine N-oxide useful in the
detergent comrocitions herein is poly(4-vinylpyridine-N-oxide) which as an average
mole II:lr weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
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Copolymers of N-vinylpyrrolidone and N-vinylimid~7QIe polymers (r~,re.lcd to
as a class as "PVPVI") are also pl~rell~d for use herein Plef~.~bly the PVPVI has
an average molec l1~r weight range from 5,000 to 1,000,000, more ~,rere.ably from
5,000 to 200,000, and most preferably from 10,000 to 20,000 (The average
mol~clll~r weight range is de~e.----lled by light scattering as described in Barth, et al.,
Chemical Analysis, Vol 113 "Modern Metho-~c of Polymer Cha-acle-i~lion'', the
flie~loSl~reS of which are iuco.~ o.aled herein by rcrere..ce.) The PVPVI copolymers
typically have a molar ratio of N-vinylim;~7Ole to N-vinylpyrrolidone from 1:1 to
0.2:1, more ~)r~rt.ably from 0.8:1 to 0.3:1, most p~erelably from 0.6:1 to 0.4:1 These copolymers can be either linear or b- ancl1ed
The present invention cG...po~;lions also may employ a polyvinylpyrrolidone
(NPVP") having an average molecular weight of from about 5,000 to about 400,000,p-~r~-ably from about 5,000 to about 200,000, and more prert.~bly from about 5,000
to about 50,000 PVP's are known to persons skilled in the dc;lel~;e.-L field; see, for
le, EP-A-262,897 and EP-A-256,696, h-co",o,~ted herein by r~re.~nce
Compositions co IA; ~ PVP can also contain polyethylene glycol (NPEG") having
an average molectll~r weight from about 500 to about 100,000, preferably from about
1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash sol lfionc is from about 2:1 to about 50:1, and more preferably from about
3:1 to about 10:1.
Suds Boosters - If high sudsing is desired, suds boosters such as Clo-C16
nol~m;des can be incorporated into the compositions, typically at 1%-10% levels
The Clo-C14 monoeth~nol and dieth~nol amides illustrate a typical class of such
suds boosters Use of such suds boosters with high sudsing adjunct surf~ct~nte such
as the amine oxides, b~; F5 and su1t~ineS noted above is also adv~nt~g-~ol~e If
desired, soluble m~npeium salts such as MgC12, MgSO4, and the like, can be addedat levels of, for " . l_, 0 1~/o-2%, to provide ~ddifion~l suds and to t~h~nce grease
removal ~e.r.-..-ance
Brighten~r - Any optical b,;~llte~ , fluorcsce~ g agents or other
b.;.~ g or wl.;lrn;lv agents known in the art can be il.co.l)o~ed in the instantcomroeitions when they are deei~ed for fabric ~ or la.~..dt.ing, at levels
typically from about 0.05% to about 1.2%, by weight, of the detergent compositions
herein. Co---,-._-~;al optical b- i,~ le~ ~ which may be useful in the present invention
can be ~l~ceified into subgroups, which inCl~lde~ but are not l~c~scc,..ily limited to,
derivatives of stilh~n~o~ pyrazoline, coumarin, carboxylic acids, ",~ll.; ~P~,ya~ es,
dilJ~ ;oLlicphene-5,5-d~ cidç~ azoles, 5- and 6-membered-ring heterocyclic
bri~ht~ners, this list being illustrative and non-limiting E~mpl~s of such brigl.~ -P ~
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are disclosed in "The Production and Application of Fluolesccnl Brighlf n;~g
Agents", M. Zahradnik Published by John Wiley & Sons, New York (1982).
Specific ~Y~mp'~~ of optical bri~htçnPrs which are useful in the present
compo~ition~ are those idçntified in U.S. Patent 4,790,856, issued to Wixon on
DecP...h~ 13, 1988. These bright~nP~s include the PHORWHITE series of
brigl.lenf;~ from Verona. Other bright~ners disclosed in this rerelcllce include:
Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-
(4-styryl-phenyl)-2H-n~phtholt 1,2-d]triazoles; 4,4'-bis- (1,2,3 -triazol-2-yl)-stil-
benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific ~Y~nnples of these
brigJ-l. n~.~ include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-ben7im;~1~7OI-2-
yl)ethylene; 2,5-bis(b~,~oxa~ol-2-yl)thiophene; 2-styryl-napth-[1,2-d]oY~7ole; and 2-
(still,~ne ~ yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued
February 29, 1972 to ~milton. Anionic bri~ht~ners are typically pler~,.lcd herein.
Coating - Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said invlediellls into a porous
hydrophobic substrate, then coating said substrate with a hydrophobic co~ting
Preferably, the detersive i"g. ed;elll is ~mixed with a surfactant before being
abso,l,cd into the porous substrate. In use, the detersive ingredient is released from
the substrate into the aqueous washing liquor, where it pelrulllls its intçn-leddetersive function.
To illustrate this technique in more detail, a porous hyd, c,phobic silica
(trademark SIPERNAT(~) D 10, Degussa) is admixed with a proteolytic enzyme
so~ltiQr ccinlA;..;-~g 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the c.~y~e/surfactant so!lltion is 2.5 X the weight of silica.
The res~llting p~wder is dispel~ed with stirring in silicQr'e oil (various silicone oil
Vi~CQ~ ;''i in the range of 500-12,500 can be used). The re~uhing silicone oil
.li.~,er:..on is emlll~ified or otherwise added to the final del~.~e.ll matrix. By this
means, ingledi~lls such as the aro,~ l;Qned enzymes, ble~hes, bleach activators,bleach catalysts, photoactivators, dyes, fluol escel ~, fabric con~itioners and
hydrolyzable surf~ct~nts can be "protected" for use in d~te~cnts, inl~lv~ling liquid
laundry de~ 5e,,l compositions.
The compositi~nc herein can contain other fluids as carriers. Low molecular
weight primary or second~ry alcohols exemplified by ~ ol, ethanol, propanol,
and isopropanol are suitable. Monohydric ~lcQhol~ are pl~r~l,ed for solubili~ingsurfactant, but polyols such as those co~ ;.-;ng from 2 to about 6 carbon atoms and
from 2 to about 6 hydroxy groups (e.g., 1,3-prlJpanediol, ethylene glycol, glycerine,
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and 1,2-plopanediol) can also be used. The compositions may contain from 5% to
90%, typically 10% to 50% of such carriers.
Bleach caealysts - If desired, compositions herein may ~d~iition5~lly
incolyol~le a catalyst or accelerator to further improve bl~ or soil removal.
Any suitable bleach catalyst can be used. For detergent compositions used at a total Y
level of from about 1,000 to about 5,000 ppm in water, the composition will typically
deliver a con~çntration of ~om about 0.1 ppm to about 700 ppm, more preferably
from about 1 ppm to about 50 ppm, or less, of the catalyst species in the wash liquor.
Typical bleach catalysts comprise a transition-metal colllp!~ , for CA~II~ one
wherein the metal co-ol~ ligands are quite resistant to l~ 7~tion and which
does not deposit metal oxides or hydroxides to any appleciable extent under the
typically alkaline conditions of washing. Such catalysts include ~ ng~n~3e basedcatalysts ~icr~osed in U.S. Pat. 5,246,621, U.S. 5,244,S94; U.S. 5,194,416; U.S.5,114,606; and EP Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al;
prërelltd examples of these catalysts include MnIV2(~-o)3(TAcN)2-(pF6)2~
MnIII2(~-0) 1 (~l-oAc)2(TAcN)2(clo4)2~ MnIV4(ll-0)6(TACN)4(Cl04)4,
MnmMnIV4-(ll-O)l~l-OAc)2-(TACN)2-(Cl04)3, MnIV~(TACN)-(OCH3)3(PF6),
and mixtures thereof wherein TACN is Llillle~llyl-1,4,7-tria_acyclono~ e or an
equivalent macrocycle; though alternate metal-co-ol~l;..A~ g ligands as well as
mononuclear complexes are also possible and monomet~llic as well as di- and
polymPt~llic co ~ ' .er and COm~JleAtS of alternate metals such as iron or n-thPni--m
are all within the present scope. Other metal-based bleach catalysts include those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of ..~ g~nçse
with various co.--~ ligands to Pnh~nce bleachin~ is also reported in the following
United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;
5,274,147; 5,153,161; and 5,227,084.
Tr~ncition metals may be pl~,CO r~ ~ or c.Jllly~ ed in-si~u with suitable
donor ligands sPIP~-~ed in function of the choice of metal, its oxiri~tiorl state and the
denticity of the ligands. Other complexes which may be inrl--ded herein are those of
U.S. Appli~tion Ser. No. 08/210,186, filed March 17, 1994.
Prell~alel Formulation - The plefelled compositions of the present invention
have a viscosity 50 cps or greater at 20~C when measured with a Brookfield
viscol.l~ler at 50 rpm with a spindle n~3, more p.-,rtl~ly of from about 50 to about
2000 cps, and still more preferably of from about 200 to about 1500 cps. Any
sl~rf~t~nt system or polymeric thiclrpner known in the art to increase the viscosity of a
composition can be used to achieve the pleÇell_d viscosity. Thus the surf~ct~ntc
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suitable to be used herein may be thicL-enin~ surf~ct~nte such as nonionic, anionic,
cationic, zwitterionic and/or amphotheric surf~ct~ntc
~ The blo~chi~ composition herein comprise water in any amount up to about
9S% by weight of the total composition. Preferably, the compositions herein will? CO~ Jl;se from about 5% to about 95%, more preferably from about 10% to about
90%, by weight of the ble~ching co",po~ilion, of water.
When the p_.o~ygtn bleach-con~ compositions accordillg to the present
invention further comprise an optional bleach activator, it is highly desired herein to
formulate said compositions either as a microemulsion or as a stable emulsion.
When forrn~ tçd as a microemulcion, the composition co",p,ises the bleach
a~lh~alor in a matrix of water, the peroxygen bleach, and h~.l,ophilic anionic and
nonionic surf~ct~nts Suitable anionic surfi~ct~ntc herein include the alkyl benzcne
s~lron~le~, alkyl s~lf~tes~ alkyl alkoxylated su!f~tec, and mixtures thereo~ Suitable
non;onic surfi~rit~ntc for use in the microemulsions herein include the hydrophilic
nonionic swr~rit~ntc as defined hcrcinaner for the emulsions accor~i"g to the present
invention.
When formul~ted as an emulsion, the composition conl~l;ses at least a
h~d~uphilic surfactant having an HLB (hydrophilic-lipophilic balance) above 10 and
at least a hydlc,phobic surfactant having an HLB up to 9, wherein said bleach
activator is Pml-lcified by said surf~ct~ntc The two dirrere.,l surfi~rit~ntc in order to
form emulsions which are stable must have dirrc,tnl HLB values, and preferably the
dirr.,.e~ce in value ofthe HLBs of said two surf~ct~ntc is at least 1, ~Icrclably at least
3. In other words, by approp~ialely colnl,ilfing at least two of said surf~ct~ntc with
dirrc, .,l HLBs in water, stable Pmlllcionc will be formed, i.e. çmlll~;onC which do not
~b~ln.~ lly sep&ale into distinct layers, upon 51~n~ for at least two weeks at 50
~C. The em~ ;onc co"" lise from about 2 % to about 50%, by weight of the total
co,.,pc- n, of said h~d.uphilic and hydrophobic surf~rt~ntc, pl~rc-ably from about
5% to about 40%, and more p.eftl~bly from about 8% to about 30%. The emulsions
cc,...~.,ise at leact about 0.1%, pr~rc,ably at least 3%, more p,crc-~-bly at least 5%, by
weight of the total emlllcion~ of one or more hydrophobic surfactant and at least
about 0.1%, p-~rclably at least 3%, more preferably at least 5%, by weight of the
f total em~ ;on~ of one or more hydrophilic surfactant. Prcr~.-ed to be used herein are
the h~l-.ph~b c l~ onic surf~ct~ntc and hydrophilic nonionic surf~rt~ntc Said
h~.olahcb c n~ n:c surf~ct~ntc to be used herein have an HLB up to 9, preferablybelow 9, more plef~.ably below 8 and said hydrophilic surf~ct~ntc have an HLB
above 10, pref~. bly above 11, more preferably above 12. .Suit~ble nonionic
~I, r~ ; for use herein include alkoxylated fatty alcohols, preferably fatty alcohol
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ethoxylates and/or propoxylates. A variety of alkoA~la~ed fatty alcohols are
cc,~ -cially available which have very di~ele,ll HLB values. For further diccllcsion
of HLB theory and its apFlir~tion to the forrnation of em~lciQnc~ please see the:
Encyclopedia of Frm~ion Technology; Becher, P., Ed.; Marcel Dekker, Inc.: New
York, 1985; Volumes 1 and 2, and lere,~;;nces cited therein.
In a particularly prefe"ed embodimPnt of the emulsion, if present, wh~:,e.~
the em~lcione co,nyl;se acetyl triethyl citrate as the bleach activator, an ~deq~-~te
non:~nic surfactant system would comprise a hydrophobic nonion;c surfactant with,
for il~cl~nr~e~ an HLB of 6, such as a Dobanolg) 23-2 and a hydrophilic nonionicsurfactant with, for jnct~ncç, an HLB of 15, such as a Dobanol~ 91-10. Other
s~lit~blE nonionic su,~-i~anL systems co"-~.,ise for ei~nlple a Dobanol~) 23-6.5 (HLB
about 12) and a Dobanol(~ 23 (HLB below 6) or a Dobanol~ 45-7 (HLB=l 1.6) and
T utencol~ TO3 (HLB=8). Dobanol~) are co"ul~e,~,;ally available nonionic
sl"rS.~,fA.. l~; available from Shell Corp. T.l-tPncol~) are co.. ~.~,;ally available
nonionic surf~ct~ntc available from BASF Corp.
The pe,~y~;en bleach-co..l~in;~ compositions according to the present
invention may further comprise an amine o~ide surfactant according to the formula
RIR2R3No, wherein each of Rl, R2 and R3 is independently a C6-C30, pl.,r1,~bly aClO-C30, most preferably a C~2-C~6 hydrocarbon chain. It has been further observed
that in a p, c~ process, the presence of said amine oxide further improves the
cle~nin~ pe,ro"--ance on particulate and/or greasy stains. It is believed that this
improve.~.enl in ele~ning p~,~""ance is matrix in-iepPn~l~Pnt To obtain either of
these be.,c~li, amine oxides, if present, should be present in ~mountc ranging from
0.1% to 10 % by weight ofthe total composition, preferably from 1.5% to 3%.
Articles of ~m-f~-re - Flefe"cd articles include the compositions herein
that are suitable for use in the processes described herein, in a pacl~e that can
provide direct app1;r~l;on of said compositions onto soiled fabrics. Pl~,f~,.lably the
cQ,.,l.Qc;l;on is p~c~aged in a pliable conl;~ r fitted with an applicator cap. ~I.it~
con~;..f-:i include those that permit applic~tion directly onto soiled fabric bysque~7ing or pouring the connpositions through the applicator cap. Such conlaille.
include those described in U. S. Pat. 4,107,067. A,~.plop,iate applicator caps include,
but are not limited to, fountain type nozzles, brush applicators, roller ball
applicators, and flip-top caps. The conlainers useful for the processes des.i,ibed
herein contain from about 4 ounces to about 32 ounces, preferably from about 4
ounces to about 24 ounces, of the compositions des-~, il.ed herein.
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The following eY~mrles illustrate the compositions of this invention, but are not
inten~ie~l to be limiting thereo~ All materials in the EAa~ ,les satisfy the functional
limitations herein.
EXAMPLE I
L The following colllyos;lions were made by mixing the listed ingredients in the listed
plOyO~ lions (weight % unless otherwise specified).
Compositions I II m IV V
Na C10-CI8 alkylc~ h~te 2 2 2 2 2
Dobanol~9 45-7 8.6 8.6 8.6 8.6 8.6
Dobanol~ 23-3 6.4 6.4 6.4 6.4 6.4
ATC 3-5 3-5 3 5 3-5 3 5
H2~2 6 6 6 6 6
BHT2 0.05 0.05 0.05 0.05 0.05
Salicylic acid1 ~- 1.5 ---- ---- ~-
Malonic acid1 ~- ---- 1.5
Glycinel ---- ---- ---- 1 ----
lt~mic acidl ~~ ~~~~ 1.5
Water and lllinols~ up to 100%
H2SO4 up to pH 4
1 fabric protection agents
* minors include perfumes, dyes, etc.
2 butylated hydroxy toluene
Composilion I comyli~es hydrogen peroxide and is free of a fabric plote~lion
agent. Compositions II to V contain a fabric protection agent which are
.~eyl~;selllali~e ofthe present invention.
The comrQsitions in Example I differ only in the identity of the fabric
pr~ ;on agent. Thus, to co---pare the tensile ~llen~ loss of fabrics treated with
pe.oArg_n blee ' ~ng COll.pO~ l;one conl~;n;~g potential fabric prol~cl;Qrl agents, this
form~ n is used as the basic pe.'~A~g~n ~le~hin~ co...po~ilion to which the
subject fabric pl ol~l;on agent is added.
EXAMPLE II
Tensile s~ ,lh test method - The tensile Sl~nglll IOSS of fabrics can be
delellllilltd by the following: Krefeld cotton ribbons (~im~n~io~ 12.5 x 5 cm2) having
a copper(2+) CQnC~ lion of 30 ppm per gram of cotton are treated with 2 ml of the
test composition accoldil)~ to FY~mple I. The test comroeitiQn is left in contact with
the ribbons for 24 hours. The ribbons are then rinsed with water, and the tensile
:~h~ lh loss measured with an INSTRON, model no. 4411. Damage on the cotton
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26
ribbons is evaluated by stretching said ribbons until they break. The force ~~c~cs~n ~ to
break the ribbons, i.e. the Ultimate Tensile Stress, is measured while the ribbons are
wet with a INSTRON, model 4411. The lower the force needed to break the cotton
ribbons, the more serious is the damage caused on the fabrics. A good co~fi~l~n~e
da,d deviation=2-4 Kg) in the results is obtained using five replicates for eachtest.
The tensile ~Lic".~;l}l loss measured above for the test composition is ~ esscd
as a p~ e and is obtained by dividing the tensile s~ of a .~rt:lenc~ cotton
ribbon, i.e. a ribbon which has not been treated with a ble~chin~ composition, by the
tensile ~ ;nglh of the test ribbon p~ ealed by the test composition.
Results are as follows:
Col--i,osilion I II III IV V
Tensile sLl~ng~ll loss (%) 69 11 19 40 45
30 ppm Copper per gram of fabric, prelre~ for 24 hours
The above results clearly show the une,~,ccltd improvement in tensile strength
loss (i.e., lower numerical values) obtained by using ble~hing compositions
according to the present invention comprising a peroxygen bleach and a fabric
pluleclion agent as compa.ed to the use of the same bleaching composition but
without a fabric plotc~,~ion agent (composition I). The tensile ~ nglh loss is
reduced when p. ~ aling fabrics with compositions accol ding to the present
invention (see comi~o~;l;QnC II to VI), even upon a prol~nged contact time, i.e., 24
hours and in presence of a high conce..L.alion of copper on the surface of said
fabrics, i.e., 30 ppm per gram of cotton fabric.
EXAMPLE III
The following compositions were made by mixing the listed ingredients in the listed
propo~ ~ions (weight % unless otherwise specified).
Composition 1 A B C
H2~2 6 6 6 6
ATC 3.5 3.5 3.5 3.5
Na C10-CI8 allylculrh~te 2 2 2 2
Dobanol 23-3 15 15 15 15
Glycinel 1 --- --- ---
Salicylic acidl ~ 1.5 ---
M~1oniG acidl ~~~ 1.5
~ t~m;~ acidl - - - 1.5
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Water and minors* up to 100%
H2S04 up to pH 4
1 fabric p.ole.;lion agent
* minors include perfumes and dyes
?.
Co.. ~o~;Lion 2 _ B C
H2~2 6 6 6 6
ATC 3-5 3-5 3 5 3 5
Na C~O-Clg alkylen1ph~te 12 12 12 12
Dobanol~ 23-3 12 12 12 12
Glycinel 1 --- --- ---
Salicylic acidl --- 1.5 --- ---
Malonic acidl --- --- 1.5 ---
i~lt~miC acidl ~~ ~~~ ~~~ 1~5
Water and minors* up to 100'~/~
H2S04 up to pH 4
1 fabric protection agent
* minors include perfumes and dyes
Composition 3 A B C D
H2~2 7 7 7 7
Na C~O-C~8 alkylc~lph~te 2 2 2 2
Dobanol~9 23-3 3 3 3 3
Glycinel 1 --- --- ---
Salicylic acidl ~ 1.5 ---
~lQn;~ acidl ~~ ~~~ 1.5
~'JIIltsltnic acidl ~ ~~~ 1.5
Water and .l.lnc":,~ up to 100
H2S04 up to pH 4
1 fabric y~t~l;On agent
* minors include perfumes and dyes
Krefeld cotton ribbons were treated with Compocitionc A to D in the same
manner as desc,ibed for the compositions in Example I.
The tensile strength loss is reduced when p. ~ c~Lu~g fabrics with Compositions
A to D ofthis ex~mple, even upon a prolonf~ed contact time, i.e., 24 hours, and in the
CA 02225l77 l997-l2-l9
W O 97/01624 PCT~US96/10938
28
,~nce of a high co~re~n~lion of copper on the surface ofthe fabrics, i.e., 30 ppm
per gram of cotton fabric.
Also when using compositions A to D on colored fabrics in the same manner as
above, no dye change and/or discoloration is observed.
