Note: Descriptions are shown in the official language in which they were submitted.
WO95/28468 ~ l ~7 3 0~ r~ 726
Deterecnt CL
This invention relates to detergent . cfJntaining a heavy metal ion
sef~uestrant amd an enzyme, wherein a meqns is provided for delaying the release to
the wash solution of said enzyme relative to the release of sqid heavy metql ion
The ~li~r~ uly removal of enzyme sensitive soils/stains such as blood, egg,
chocolate, gravy from soiled/stained substrates is a particular challenge to theformulator of a detergent ~C~ for use in a washing method such as a laundry
or machine di~l,w ' ~ method.
Commonly, the removal of such soils/stains has been enabled by the use of enzyme~""'1"' '~` proteolytic, amylolytic, cellulolytic and lipolytic enzymes.
A problem ~ ' with the use of such enzymes in washing methods is the
propensity of these enzymes to be affected by the presence of other detergent
- r ' in the wash solution. ~f ~p~iq~ n of enzymes by for example, bleach
- - r c~in be a particular problem
The Applicants have found that enzyme ~I~c.,- l-~;.,., may be accelerated by thepresence of heavy metal ions in the wash solution.
Whilst reducing the effects of enzyme df ~ ;. . can to an extent be countered byincreasing the level of enzyme added to the wash solution this involves additional use
of what are expensive detergent
The Applicants have now however found that where a u. ,~ n cont~uning both a
heavy metal ion sequestrant and an enzyme is employed, and wherein a me~ms is
provided for delaying the release to a wash solution of the enzyme relative to the
release of the heavy metal ion sequestrant the problem of enzyme ~i ~;"..I-'i-) l may be
woss/2s46s 21 87~0~ r~ 6
.. 1;....-~ 1 Hence, enhanced stain/soil removal may be obtained without the need to
increase the level of enzyme to counter the effects of enzyme ~IP~r7~
The Applicants have in addition found that stain/soil removal benefits may be
obtained when a soiled substrate is pretreated with a solution containing a heavy metal
ion . t, and optionally a water soluble builder, prior to being washed in a
method using an enzyme containing detergent product.
It is therefore an object of the present invention to provide l . suitable for
use in laundry and machine ~" ' ... ' ~ methods having enhanced stain removal
without neP~ding to employ high levels of enzymes.
It is a related object of the present invention to provide a stain/soil 1.. :.~.. 1
method involving pretreating the soiled substrate with a solution containing a heavy
metal ion sequestrant and optionally a water soluble builder, prior to washing with an
enzyme containing detergent product.
~I~mnl~ry of the InVpn~ n
According to the present invention there is provided a detergent .
containing
(a) a heavy metal ion ~ and
(b) an enzyme
wherein a means is provided for delaying the release to a wash solution of said
enzyme relative to the release of said heavy metal ion sequestrant such that in the T80
test method herein described the time to achieve a ~-- that is 80% of the
ultimate ~ of said heavy metal ion sequestrant is less than 60 seconds and
the time to achieve a c- ,. . ' ., ' ;~ ~ that is 80% of the ultimate c ~ of said
enzyme is more than 90 seconds.
According to an especially preferred aspect of the present invention said ~ ~,1 . .,~ -~; l ;-
addi~io~ally contains
(c) a water soluble builder
w09sl28468 2~73~2 P~ 6
wherein a means is provided for delaying the release to a wash solution of said
enzyme relative to the release of said water soluble builder such that in the TSO test
method herein described the time to achieve a ~ that is 50% of the
ultimate ~ oF said water soluble builder is less than 60 seconds.
According to amother aspect of the present invention there is provided a washingmethod comprising the steps of:
(1) applying an enzyme-free solution of a ~ containing a heavy metal
ion ~-oq~ch~rlf to a soiled substrate;
(2) allowing said solution to remain in contact with said soiled substrate for an
effective time interval;
(3) washing said soiled substrate using a washing method involving use of an
enzyme-containing detergent c
Heavy ~Pt~l ion sequestra~
The detergent ~ of the invention contain a heavy metal ion ; By
heavy metal ion sequestrant it is meant herein c~ which act to sequester
(chelate) heavy metal ions. These ~ may also have calcium and
chelation capacity, but ~... F .~1; -lly they show selectivity to binding heavy metal ions
such as iron, manganese and copper.
Heavy metal ion ~ are generally present at a level of from 0.005% to 20%,
preferablyfromO.1% to 10%, morepreferablyfromO.25% to7.5% andmost
preferably from 0.5% to 5% by weight of the ~
Heavy metal ion ~- 1u ~ which are acidic in nature, having for example
I ' . ' acid or carboxylic acid ~ ' may be present either in their acid
form or as a complex/salt with a suitable counter cation such as an alkali or allcaline
metal ion, or substituted ion, or any mixtures thereof.
Preferably any salts/complexes are v~ater soluble. The molar ratio of said counter
cation to the heavy metal ion sequestrant is preferably at least 1:1.
wo ss/2s46s
7 1 ~73~2 P~ 6
Suitable heavy metal ion I for use herein include organic I ' . '
such as the amino allAylene poly (alkylene I ' , ' ), alk~li metal ethane 1-
hydroxy f q'-q' and nitrilo ~ .._.llyl...~ L
Preferred among the above species are diethylene triamine penta (methylene
~ ' . ' ), ethylene diamine tri (methylene ~ A,...._ hJl..l~ diamine
tetra (methylene I ' , ' ) and hydroxy-ethylene 1,1 dir' . '
Other suitable heavy metal ion sequestrant for use herein include .- ' . ;l. .~ acid
and pol~ - buAylic acids such as ~lLJl~ ' '- J~ acid,
pentacetic acid, elllyl~ . disuccinic acid, t~
diglutilric acid, 2~ d1UAY~IU~ ' disuccinic acid or any salts thereof.
Especially preferred is c;~.yl 1 N,N'-disuccinic acid (EDDS) or the aLkali
metal, alkaline earth metal, or substituted salts thereof, or
mixtures thereof. Preferred EDDS . ' are the free acid form and the sodium
or ~ salt or complex thereof. Examples of such preferred sodium salts of
EDDS include Na2EDD' snd Na3EDDS. Examples of such preferred
compleAes of EDDS inchaie MgEDDS and Mg2EDDS.
Other suitable heavy metal ion ,~ t~ for use herein are; ~ acid
derivatives such as 2 h.1dluA~ l diacetic acid or glyceryl imino diacetic acid,
described in EP-A-317,542 and EP-A-399,133.
The - " acid-N-2-l.rdluA~,lu~l sulfonic acid and aspartic acid N-
~.~LIbUA~ 1 N-2-l,~dluAy~,lul,~1-3-sulfonic acid ~ described in EP-A-
516,102 are also suitable herein. The ,3-alanine-N,N'-diacetic acid, aspartic acid-
N,N'-diacetic acid, aspartic acid ~ acid and ' - acid
described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based c, ~ EP-A-510,331 describessuitable . derived from collagen, keratin or casein. EP-A-528,859
describes a suitable alkyl " acid cPq~ tt~nf Dipicolinic acid and 2-
I ' . ' ' 1,2,4-lli~UA~ acid are alos suitable. Cl~, ' N,N'-
disuccinic acid (GADS) is also suitable.
Enzyme
wo 95/28468 2 1 8 7 3 0 2 1 ~ 6
s
The détergent c~ u~ Ac contain an enzyme. Suitable enzymatic materials include
the cu.~ lly available lipases (that is enzymes having lipolytic activity), amylases
(that is, enzymes having amylolytic activity), neutsl and alkaline proteases (that is,
enzymes having proteolytic activity), estesses, cellulases (that is, enzymes having
cellulolytic activity), pectinases (that is, enzymes having pectolytic activity), lactases
(that is, enzymes having lactolytic activity) and ~,.u,.iJ~c-~ ~;u,.~, "y
' into detergent c, ~ Suitable enzymes are discussed in US
Patents 3,519,570 and 3,533,139.
Preferred ~ lly available protease enzymes include those sold under thetsdenames Alcalase, Savinase, Primase, Duszym, and Espesse by Novo Industries
A/S (Denmark), those sold under the tsdename Maxatase, Maxacal and Maxapem by
Gist-Brocades, those sold by Genencor T ~ l and those sold under the
tsdename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
UII ' into the . ~ in ~ ' with the invention at a level of from
0.0001% to 4% active enzyme by weight of the c~
Preferred amylases include, for example, a-amylases obtained from a special strain of
B l . r , described in more detail in GB-1,269,839 (Novo). Preferred
..,;ally available amylases include for example, those sold under the tradename
Rapidase by Gist-Brocades, and those sold under the tsdename Termamyl and BAN
by Novo Industries A/S. Amylase enzyme may be . ' into the ~ ,u-:~
in accordance with the invention at a level of from 0.0001% to 2% active enzyme by
weight of the .~
Lipolytic enzyme (lipase) may be present at levels of active lipolytic enzyme of from
0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably
from 0.001% to 0.5% by weight of the r-.
The lipase may be fungal or bacterial in origin being obtained, for example, from a
lipase producing strain of ~miçQL sp., Tl,~ ",,s sp. or r~....1.,".~." ~ Sp.
including ~vJu ~ sP-ldo~lc~lige~s or p~pl~rll~mqr~ fluorescens. Lipase from
chemically or genetically modified mutants of these stsins are also useful herein.
A preferred lipase is derived from ~ v~ ù~ l c.. ~ 5. which is
described in Gsnted European Patent, EP-B-0218272.
wos~28468 2~7~ P~ 1.6
Another preferred lipase herein is obtained by cloning the gene from E~m~
lanuyinos_ and expressing the gene in Asver~ c Q~Yza, as host, as described in
European Patent ~rrliratif~n, EP-A-0258 068, which is: lly available from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase
is also described in U.S. Patent 4,810,414, HLb_ J~ ,.. et al, issued March 7, 1989.
Fn7yme St~l ili7i.~p SyctPm
Preferred enzyme-containing, . herein may comprise from about 0.J01%
to about lCi%, preferably from about 0.005% to about 8%,most preferably from about
0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme
stabilizing system can be any stabilizing system which is compatible with the detersive
enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propyleneglycol, short chain carboxylic acid, boronic acid, and mixtures thereof. Such
stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible
protease inhibitors.
The ~ herein may further comprise from 0 tf~ about 10%, preferably fromabout 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent
chlorine species present in many water supplies from attacking and ;~ Liv the
enzymes, especially under alkaline conditions. While chlorine levels in water may be
small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available
chlorine in the total volume of water that comes in contact with the enzyme during
washing is usually large; dCWI-li~l~ly, enzyme stability in-use can be ~ d~
Suitable chlorine scavenger anions are widely available, and are illustrated by salts
containing cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.,~ntifl~ ntc such as carbamate, ascorbate, etc., organic amines such as
acid ~EDTA) or alkali metal salt thereof, ' ~'
~MEA), and mixtures thereof can likewise be used. Other w~ ..iollal scavengers
such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium
perborate t~ d~y~' , sodium perborate lllollull~.ll.lt., and sodium ~.~L as
well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate,
malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
WO 95/28468
~1 8 7 3 ~ 6
E2PI~tive rPIP~p I ' ~tir~
In an essential aspect of the invention a means is provided for delaying the release to a
wash solution of the enzyme relative to the release of the heavy metal ion ~
Said means may comprise a means for delaying the release of the enzyme to the wash
solution.
'y said means may comprise a means for enhancing the rate of release of
the heavy metal ion sequestrant to the solution.
Delayed r~tP of rPlp~cf~ - mça~
The delayed release means can include coating the enzyme with any suitable
component with a coating or mixture of coatings designed to provide the delayed
release. The coating may therefore, for example, comprise a poorly water solublematerial, or be a coating of sufficient thickness that the kinetics of dissolution of the
thick coating provide the controlled rate of release.
The coating material may be applied using various methods. Any coating material is
typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2,
preferably from 1:49 to 1:9.
Suitable coating materials include l.iol.y.cli~cs (e.g. partially) Il,~dll 0 ' vegetable
oil, soy bean oil, cotton seed oil) mono or d;ol~lid~ l~ly~l~lline wa~es,
gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth metal
sulphates, silicates and carbonates, including calcium carbonate.
Preferred coating material is sodium silicate of SiO2: Na2O ratio from 1.6: 1 to 3.4
: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of from 2% to
10%, (normally from 3% to 5%) of silicate solids by weight of the ~.
M.~ silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder materials
to provide composite inorganic ~1~ binder coatings. Suitable binders include
wossl2s46s 2 ~ 8 7~ ~ r~l,u~ 6
the ClD-C20 alcohol ethoxylat~w containing from 5 - 100 moles of ethylene oxide per
mole of alcohol and more preferably the Cls-C20 primary alcohol ethoxylates
containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders incluoe certain polymeric materials. rolJ ~ Jl~ulidul~w
with an average molecular weight of from 12,000 to 700,000 and ~)UIJ~ glycols
(PEG) with an average molecular weight of from 600 to 10,000 are examples of such
polymeric materials. Copolymers of maleic anhydride with ethylene, Ill.,tll~l~;..yl
ether or ' .~ acid, the maleic anhydride ~.... I;t.~ .g at least 20 mole percentof the polymer are further examples of polymeric materials useful as binder agents.
Thewe polymeric materials may be used as such or in ~ - with solvents such
as water, propylene glycol and the above mentioned Clo-C20 alcohol ethoxylates
containing from 5 - 100 moles of ethylene oxide per mole. I~urther examples of
binders include the Clo-C20 mono- and diglycerol ethers and also the Clo-c2o fatty
acids.
Cellulose derivatives such as methylcellulose, C.llbU~ LJ' " ' , ethyl
l~dlu~ .,llulose and l~ u~ cllulose, and homo- or co-polymeric
pol~ ubu~.yli~, acids or their salts are other examples of binders suitable for use
herein.
One method for applying the coating material involves aGc~ Preferred
~v~l.. ~1;.. ,. procewses include the use of any of the organic binder materials
described ~.~i~.~uv~. Any cu..~..liù..41 ~ee - ~I may be used including,
but not limted to pan, rotary drum and vertical blender typ_s. Molten coating
may alsû be applied either by being poured onto, ûr spray atomized onto
a moving bed of bleaching agent.
Other means of providing the required delayed release include mechanical means for
altering the physical h_~-- h ;~ of any enzyme containing particulate to control its
solubility and rate of release. Suitable protocols could include .
mechanical injection, manual injection, and adjustlnent of the solubility of the bleach
compound by selection of particle size of any particulate cn lrnPnt
Whilst the choice of particle size will depend both on the c-. ~ of theparticulate comrnPnt~ and the desire to meet the desired delayed release kinetics, it is
wo g5n8468 2 ~ ~ 7 3 D~ F~ 6
9
desirable that the particle size should be more than 500111;.,1~ , preferably
having an average particle diameter of from 800 to 1200 I.~
Additional protocols for providing the means of delayed release include the suitable
choice of any other l , of the detergent ~ ;.... matrix such that when
the ~.,. .1...~ l,.,.. is introduced to the wash solution the ionic strength ~..v;.,
therein provided enables the required delayed release kinetics to be achieved.
i~nced rate of r~ c~ - me3~
All suitable means for enhancing the rate of release of the heavy metal ion sequestrant
to the solution are envisaged.
The enhanced release means can include coating any suitable component with a
coating designed to provide the enhanced release. The coating may therefore, forexample, comprise a highly, or even el~~ " water soluble material.
Other means of providing the required delayed release include mechanical means for
altering the physical ~ of the heavy metal ion sequestrant to enhance its
solubility and rate of release.
A suitable protocol could include deliberate selection of the particle size of any heavy
metal ion sequestrant containing . - . -- The choice of particle size will depend
both on the . , of the particulate . t, and the desire to meet the
desired enhanced release kinetics. It is desirable that the particle size should be less
than 1200 III;~,IUII.~,~15, preferably having an average particle diameter of from 1100
to 500 ~ .lulrl~t~
Additional protocols for providing the means of delayed release include the suitable
choice of any other . of the detergent f ,, ~ ;-- matrix, or of any
particulate component containing the heavy metal ion . t, such that when the
is introduced to the wash solution the ionic strength ~ ,..i therein
provided enables the required enhanced release kinetics to be achieved.
R~ ive I of rr~ kinl~ir
-
W0 95/28468 2 ~ 3 ~ 3 1~ ~ P~
The release of the peroxyacid bleach component from the enzyme relative to that of
the heavy metal ion se~uestrant component is such that in the T80 test method herein
desc-fibed the time to achieve a ~ ",r~ ,l,AI;.,n that is 80% of the ultimate ~
of said heavy metal ion se~uestrant is less than 60 seconds, preferably less than 50
seconds, more preferably less than 40 seconds, and the time to achieve a
f UI I. . . ~ that is 80 % of the ultimate of said enzyme is more than
90 seconds, preferably from 90 to 240 seconds, more preferably from 100 to 200
seconds, most preferably from 120 to 180 seconds.
The ultima~e wash ~ of the heavy metal ion se~uestrant is typically from
0.0001% to O.OS % by weight, but preferably is more than O.OJI %, more preferably
more than 0.002% .
Where the enzyme is a protease, the ultimate amount in a typical wash solution is
from 0.1 to 100 ICNPU, but preferably is from 0.5 to 50 KNPU, more preferably
from 3 to 30 KNPU and most preferably from 6 to 30 KNPU.
Where the enzyme is an amylase, the ultimate amount in a typical wash solution is
from I to 200 KNU, but preferably is from 10 to 100 KNU, more preferably from 40to 80 KNU.
Where the enzyme is a lipase, the ultimate amount in a typical wash solution is from I
to 300 KLU, but preferably is from 10 to 2J0 KLU, more preferably from 10 to 100KLU.
Where the enzyme is a cellulase, the ultimate amount in the wash is typically from 1.0
to 1200 CEW, but preferably is from S0 to 1.)00 CEW, more preferably from 80 to
500 CEW.
D~laved rf~lf~cf~ - test rnf ~hnfl
The delayed release kinetics herein are defined with respect to a 'TA test method'
which measures the time to achieve A% of the ultimate c~ 'level of that
component when a ~ ; " containing the component is dissolve~i according to
the standar~ conditions now set out.
~vo
g~28468 ~ ~ 37~2 P~_l/l /0:~726
11
The standard conditions inYolve a 1 litre glass beaker filled with 1000 ml of distilled
water at 20C, to which lOg of ~ is added~ The contents of the beaker are
agitated using a magnetic stirrer set at 100 rpm. The magnetic stirrer is pea/ovule-
shaped having a maximum dimension of l.5cm and a minimum dimension of O.5cm.
The ultimate /level is taken to be the ~-- 'level attained 10
minutes after addition of the f.'- '~ to the water-filled beaker.
Suitable analytical methods are chosen to enable a reliable ~ of the
incidental, and ultimate in solution ~ of the component of concern,
subsequent to the addition of the c~ u-:~ to the water in the beaker.
Such analytical methods can include those involving a continuous monitoring of the
level of ,-.~ ;.." of the . t, including forexample ~ and
~'V~A'-- 1~ -- II;f methods.
Alternatively, methods involving removing titres from the solution at set time
intervals, stopping the ~' ' process by an a~ means such as by rapidly
reducing the ~ of the titre, and then .' ~ the f -''l( ' " of the
component in the titre by any means such as chemical titrimetric methods, can beemployed.
Suitable graphical methods, including curve fitting methods, can be employed, where
ul , to enable calculation of the the TA value from raw analytical results.
. The particular analytical method selected for ~ , the ~ of the
t, will depend on the nature of that . . t, and of the nature of the
containing that:
Water-soluble builder com~ound
The detergent , of the present invention may contain as a highly preferred
component a water-soluble builder compound, typically present at a level of from 1%
to 80% by weight, preferably from 2% to 60% by weight, most preferably from 2%
to 40% by weight of the . (.. lln.~
In a highly preferrcd aspect of the invention a means is also provided for delaying the
release to a wash solution of the bleach relative to the release of the preferred water
. _ _ . . _ . . . _ .. . .. _ . . . . . . _ ..... _ .. .... .. . . . ... . .... . ... . .. . ... , ... _
WO 9~128468 P~ 6
.2~ 873~i2 ~
12
soluble builder ~ r ' Said means can comprise equivalents of any of the
delayed release means herein described for achieving the delaycd release of the bleach
described k. .1 :..1,~ ~...,
Said delayed relcase means is preferably chosen such that in the T50 test methodherein described the time to achieve a .,, .1,~l;.)., that is 50% of the ultimate
. - - of said water soluble builder is less than 60 seconds, preferably less
than 50 seconds, more preferably less than 40 seconds.
The ultimate wash ~ of the water-soluble builder is typically from
0.0005% to 0.4%, preferably from 0.005% to 0.35%, more preferably from 0.01%
toO.3%.
Suitable water-soluble builder, . ' include the water soluble monomericpVl.y~UA~- or their acid forms, horno or copv~ , pOI~lbuA,~liC acids or
their salts in which the IJul~bvAylic acid comprises at lcast t vo carboxylic radicals
separated from each other by not more that two carbon atoms, carbonates,
b;WI~ borates, I ' . ' silicates and mixtures of any of the foregoing.
The ~IJUA~- or pVI~l.VA.yl.Lt~ builder can be or oligomeric in type
although - PVIY~UA.~ are generally preferred for reasons of cost and
Suitable ~VUA~' containing one carboxy group include the water soluble salts of
lactic acid, glycolic acid and ether derivatives thereof. r~l~bvA~ldh~ containing
two carboxy group Iclude the water-soluble salts of succinic acid, malonic acid,(~II~I~..~I;VAy) dia~tic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid
and fumaric acid, as well as the ether ~UA~' and the sulfinyl ~buAy'
roly~buA~' containing three carboxy groups include, in particular, water-solublecitrates, aconitrates and as well as succinate derivatives such as the
..I~ lUAy described in British Patent No. 1,379,241,
la.,tvA~ described in British Patent No. 1,389,732, and:
described in ~ .L,.I/ Application 7205873, and the ui~lJvly~buAy' materials
such as 2~xa-1,1,3-propane L-i~l,v~' described in British Patent No.
1,387,447.
woss/28468 2~ 2
POIYWIJVA~- containing four carboxy groups include UAy,' disclûsed in
British Patent No. 1,261,829,1,1,2,2-ethane t~L,d~uA~' 1,1,3,3-propane
Ltld~ul UAy' - and 1,1,2,3-propane t~tld~dllJuAy' rV~ UAyldt~a containing
sulfo ~ include the 1r derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,4æ and in U.S. Patent No. 3,936,448, and the sulfonatedpyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and ll~t~,lv~ ,lic ~vlywbuAyldt~ include ~, ' . -cis,cis,cis-t~ JUAyl~.t~_s, ~. ~ 2,3,4,5 ~hdll~ - cis,
cis, cis ~ VAyldt~l~ 2,5; ~, - cis - V;~UA~ 2,2,5,5-
ydl~ - b~tl~ uAy- i, 1,2,3,4,5,6-hexane-1~ and
~buAy~ ,;hyl derivatives of polyhydric alcohols such as sorbitol, mannitol and
xylitol. Aromatic pVl~wl,VA~ include mellitic acid, luy~ ,lliLc acid and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred pVl~W~UA~ are ll~dluAy~lJuAJ- containing upto three carboxy groups per molecule, more ~ citrates.
The parent acids of the . - or oligomeric p~ ~bu~- chelating agents or
mixtures thereof with their salts, e.g. citric acid or '~ ;c acid miAtures are also
. ~ as useful builder ~ ....t~
Borate builders, as well as builders containing borate-forming materials that can
produce borate under detergent storage or wash conditions can also be used but are
not preferred at wash conditions less that about 50C, especially less than about
40C.
Examples of carbonate builders are the alkaline earth and alkali metal ~ ' ,
including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine
calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the al~ali metal vlyl ' , ' s, sodium, potassium and ~ sodium and
potassium arld ~ r~ , ' ', sodium and potassium ~ . ' . ,
sodium polymeta/phosphate in which the degree of IJVI~ iLd~iUII ranges from about
6 to 21, and salts of phytic acid.
w095/28468 2 1 873~ r~l,u. ,~6
Suitable silicates include the water soluble sodium silicates with an SiO2: Na20 ratio
of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being
most preferred. The silicates may be in the form of either the anhydrous salt or a
hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most preferred
silicate.
Silicates are preferably present in the detergent; . in accord with the
invention at a level of from 5% to 50æ by weight of the . more
preferably from 10% to 40% by weight.
Aririitinnq~ u~
he detergent . . of the invention may also contain additional detergent
The precise nature of these additional ~ r ', and levels of
i.~c~ u.~.lio~ thereof will depend on the physical form of tbe ~u",~ ;..,\ and the
nature of the cleaning operation for which it is to be used.
The c. ~ ''' of the invention may for example, be formulated as hand and
machine laundry detergent ~ including laundry additive ~ ;.."c and
C'U~ suitable for use in the 1~ ~. r- " , 1 of stained fabrics and machine
When formulated as C~ suitable for use in a machine wasbing method, eg:machine laundry and machine d;~h~ ' ~ methods, the ~iu,..~ iu":, of the invention
preferably contain one or more additional detergent . . selected from
builders, organic polymeric ~ . ' bleaches, suds . r L~ UI~ lime
soap ~ nt~, soil suspension and anti~ agents and corrosion inhibitors.
Laundry . 1, can also contain, as additional detergent . . softening
agents.
Surfactant
The detergent ~ Of the invention may contain as an additional detergentcomponent a surfactant selected from anionic, cationic, nonionic ampholytic,
t~ . ;. and L.~i.t~,liu..;c, surfactants and mixtures thereof.
Wo9S/28468 , 1 a73~2 ~ 726
' ' 15~ '
The surfactant is typically present at a level of from 0.1% to 60% by weight. More
preferred levels of i ~ of surfactant are from 1% to 35 % by weight, most
preferably from 1% to 20% by weight.
The surfactant is preferably formulated to be compatible with any enzyme
present in the ~ p~ ;.. In liquid or gel ~ the surfactant is most
preferably formulated such that it promotes, or at least does not degrade, the stability
of any enzyme in these
A typical listing of anionic, nonionic, ampholytic, and LW"' classes, and
species of these c~lrf~rt~llt~, is given in U.S.P. 3,929,678 issued to Laughlin and
Heuring on December 30, 1975. Further examples are given in ~Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of
suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March
31, 1981.
Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used
in ' with one or more anionic and/or nonionic - r
.Aninnir suff~.~t~^t
Essentially any anionic surfactants useful for detersive purposes can be included in the
These can include salts (including, for example, sodium, potassium,
and substituted: salts such as mono-, di- and i '
salts) of the anionic sulfate, sulfonate, .,~l,w~ and sarcosinate - '-
Other anionic surfactants include the ~ such as the acyl -- ' N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinates and C..lf-- -
of '~ (especially saturated and ~ ' C12-C18
) diesters of '~ (especially saturated and I ~ C6-C14
diesters), N-acyl ~, Resin acids and h~ - O ' resin acids are also
suitable, such as rosin, I.~JI. O ' rosin, and resin acids and llydl~ O ' resin
acids present in or derived from tallow oil.
Aninni~ c~lf~t.e surfactant
wo gs/2s46s 2 1 87 3 Q 2 . ~ c6
Anionic sulfate surfactants suitable for use herein include the linear and branched
primary alkyl sulfates, alkyl ~ v~y '' fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide ether 5ulfates, the Cs-C17 aCYI-N-(CI-C4 alkyl) and -N-(CI-c2
hydroxyalkyl) glucamine sulfates, and sulfates of all-yll,vl~- .1. -. ;.1. ~ such as the
sulfates of ~ JVIY~IU~U ,;Je (the nonionic r ' ~ beirg described
herein).
Alkyl ~lh~A~ '~ ' surfactants are preferably selected from the group consisting of
the C6-CIg alkyl sulfates which have been ~ u~' ' with from about 0.5 to about
20 moles of ethylene oxide per molecule. More p~eferavly, the alkyl .,;.hvi~y rsurfactant is a C6-CI~ alkyl sulfate which has been ~ vi~yl~,~ with from about 0.5
to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per
molecule.
W095/28468 2~813Q~ 726
. I
17
An~ clllfn 'tf~ c~factant
Anionic sulfonate surfactants suitable for uæ herein include the salts of Cs-C20linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
aLkane sulfonates, C6-C24 olefin sulfonates, sulfonated ~ ~ubu~yli~ acids, alkylglycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and
any mixtures thereof.
Anionic ~u~ , cl~rf~
Anionic ~ u~' surfactants suitable for use herein include the alkyl ethoxy
wl~ .y' , the alkyl polyethoxy POI~ JA.~ ' surfactants and the soaps ('alkyl
carboxyls'), especially certain æcondary soaps as described herein.
Preferred alkyl ethoxy ~1,~ ' for uæ herein include those with the formula
RO(CH2CH20)X CH2C00-M+ wherein R is a C6 to Clg alkyl group, x ranges from
O to 10, and the ethoxylate ,' ' is such that, on a weight basis, the amount of
material where x is 0 is less than about 20 %, and the amount of material where x is
greater than 7, is less than about 25 %, the average x is from about 2 to 4 when the
average R is C13 or less, and the average x is from about 3 to 10 when the average R
is greater than C13, and M is a cation, preferably choæn from alkali metal, alkaline
earth metal,: mono-, di-, and tri~ most preferably
from sodium, potassium, and mixtures thereof with ~ Pcil-rn ions. The
preferred alkyl etho:~y ~Ub~A.~' ' are thoæ where R is a C12 to Cl~ alkyl group.
Alkyl polyethoxy ~l~u~u,-~k,t~ surfactants suitable for use herein include thosehaving the formula
RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to C1g alkyl group, x is from 1 to 25,
R1 and R2 are selected from the group consisting of hydrogen, methyl acid radical,
succinic acid radical, I.~ ,U~..,;..;., acid radical, and mixtures thereof, wherein at
least one Rl or R2 is a succinic acid radical or l~.rdlu~J acid radical, and R3
is ælected from the group consisting of hydrogen, substituted or, ,I.~
h~d~u~bo~ having between 1 and 8 carbon atoms, and mixtures thereof.
W095/2846~ r. ~ 6
2 1 873~2
18
Anir,nic c:~rnnrlqy :~lq,7 surfqr q~t
Preferred soap surfactants are secondary soap surfactants which contain a carboxyl
unit connected to a secondary carbon. The secondary cqrbon can be in a ring
structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl
~i.u,.~' The secondary soap suAactants should preferably contain no ether
linkages, no ester lirlkages and no hydroxyl groups. There should preferably be no
nitrogen atoms in the head-group (,q~rhirhilir rortion). The secondary soap
suAactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up
to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred secondary
soap ~ r~
A. A highly preferred class of secondary soaps comprises the secondary carboxyl
materials of the formula R3 CH(R4)CooM, wherein R3 is CH3(CH2)x and
R4 is CH3(CH2)y, wherein y can be O or an integer from I to 4, x is an integer
from 4 to 10 and the sum of (x f y) is 6-10, preferably 7-9, most preferably 8.
B. Another preferred class of secondary soaps comprises those carboxyl
c~ , ' wherein the carboxyl substituent is on a ring ~I~J~ l unit,
i.e., secondary soaps of the formula R5-R6-CooM, wherein R5 is C7-C10,
preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene,
cy~,lu~.~ and ."yl ' ' (Note: RS can be in the ortho, meta or para
position relative to the carboxyl on the ring.)
. Still another preferred dass of secondary soaps comprises secondary carboxyl
' of the formula CH3(cHR)k-(cH2)m-(cHR)n-
CH(COOM)(CHR)o~(CH2)p~(CHR)q~CH3~ wherein each R is Cl-C4 alkyl,
wherein Ic, n, o, q are integers in the range of 0-8, provided that the total
number of carbon atoms (including the ~ ' ) is in the range of 10 to
18.
In each of the above formulas A, B and C, the species M can be any suitable,
especially water-~nl~hili7ing" counterion.
I~specially preferred secondary soap suAactants for use herein are water-soluble
W095/28468 7~87~a2 P~,l/U~,'Q3726
19
members selected from the group consisting of the water-soluble salts of 2-methyl-1-
undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-
octanoic acid and 2-pentyl-1-heptanoic acid.
All~i mf~l C~lrn~inate surfactant
Other suitable anionic surfactants are the alkali metal ~, of formula R-CON
(Rl) CH2 COOM, wherein R is a Cs-C17 linear or branched alkyl or alkenyl group,
Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and oleyl methyl ~, in the form of their sodium salts.
~ surf~rf~-~t
Essentially any anionic surfactants useful for detersive purposes can be included in the
Exemplary, non-limiting classes of useful nonionic surfactants are listed
below.
Nnnir,nir ~IyhyJlu~y fq'tY ~rif~ amide surfact,a~
Poly;.yJ.u,.y fatty acid amides suitable for use herein are those having the structural
formula R2CONRIZ wherein: R1 is H, Cl-C4 l~yJIu~ubyl~ 2-hydroxy ethyl, 2-
hydroxy propyl, or a mixture thereof, preferable Cl-C4 alkyl, more preferably Cl or
C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a Cs-C31 I~ u~yl,
preferably ~ Cs-C1g alkyl or aLicenyl, more preferably straight-chain Cg-
C17 alkyl or alkenyl, most preferably straight-chain C1 1-Cl7 alkyl or alkenyl, or
mixture thereof; and Z is a pul~h~J-u~hyd-u~l~l having a linear l-ydlu~ul-,yl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
(preferably ~;LI~u~y' ' or ~u~u~' ') thereof. Z preferably will be derived from a
reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nnninnir ~ ' of ~IkYI
The POI~LI.J~ pol~l -u~ , and polybLI~ylu..~ oxide c(." 1~ t` ` of alkyl
phenols are suitable for use herein. In general, the pol~,Lh~ oxide ~-- '- -
are preferred. These . ~ ~ include the ' products of alkyl phenols
having an alkyl group containing from about 6 to about 18 carbon atoms in either a
straight chain or branched chain ~-..,.',~ .,l;.... with the alkylene oxide.
W095128468 2~73~12 I~l/U~ I~6
Nonionic ethoxyl~ed alcohol surf~rt~nt
The alkyl ethoxylate ~ products of aliphatic alcohols with from about I to
about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or secondary, and
generally contains from 6 to 22 carbon atoms. Pal~h,ulally preferred are the
~r.~.~.l. r. .l;.~n products of alcohols having an alkyl group containing from 8 to 20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
Nonionic ~ uvu~ f~tty alcohol surf~e~
The ~ uAyldt~l C6-Clg fatty alcohols and C6-CIg mixed ~:LI~u~l.~-~/ululuu~
fatty alcohols are suitable surfactants for use herein, ~aui ' ~y where water soluble.
Preferably the ell.uA~l~t~i fatty alcohols are the C1o-CIg ~ u~.~' ' fatty alcohols
with a degree of ~Ihw~iul~ of from 3 to 50, most preferably these are the C12-C18
IU/~' ' ' fatty alcohols with a degree of G~hu~la~iun from 3 to 40. Preferably the
mixed ~I.u~ ,.u~u,~ ' fatty alcohols have an alkyl chain length of from 10
to 18 carbon atoms, a degree of ~ u.~laLiull of from 3 to 30 and a degree of
,UlU,UW~ iUll of from 1 to 10.
Nonionic EO/PO - ' ~ witl ~rop~lene ~IYCI
he, ' products of ethylene oxide with a II,~d-U~Ul-U~ base formed by the
of propylene oxide with propylene glycol are suitable for use herein.
The 1-~ ' portion of these . , ' preferably has a molecular weight of
from about 1500 to about 1800 and exhibits water insolubility. Examples of
' of this type include certain of the ~;ully-available PluronicTM
- '- marketed by BASF.
~r~nir~ni~ E0 ~,...1 . I;,", ~roducts with vropylene u,.;du/~ rii~minl~ adducts
The . ' products of ethylene oxide with the product resulting from the
reaction of propylene oxide and ~ r~r-~ are suitable for use herein. The
h~d~ ~ moiety of these products consists of the reaction product of
~ny' - ' and excess propylene oxide, and generally has a molecular weight of
WO 95/284C8 2 ~ ~ 7 3 ~ 2 P~ 6
21
from about 2500 to about 3000. Example5 of this type of nonionic surfactant include
certain of the ~,u~ lly available TetronicTM ~ . ' marketed by BASF.
Nonionic ~IkylyOl~a~ idc surfactant
Suitable alh~,lyùl~ for use herein are disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a l.yJ..r' ' - group containing from about
6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a
,ul~ll~i,l~, e.g., a pol~ .os;d~, hydrophilic group containing from about 1.3 toabout 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide containing S or 6 carbon atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the
glucosyl moieties. (Optionally the l~JIu~ , group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or ~al~ tnQ;~ir )
The; r " .. . h~, ;r1r bonds can be, e.g., between the one position of the additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide
units.
The preferred alk.yll,ul~ .,u~id~s have the formula
R20(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alk~',j yl, hydroxyalkyl,
hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10
to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10,
preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from
1.3 to 2.7. The glycosyl is preferably derived from glucose.
Nonionic f~t~y acid ~mifir s~ rt~nt
Fatty acid amide surfactants suitable for use herein are those having the formula:
R6CoN(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen,
Cl-C4 alkyl, Cl-C4 l~yJIw~y~lkyl~ and -(C2H40)XH, where x is in the range of from
1 to 3.
A ' surfactant
wo sst2846s 2 1 8 ~ 3 ~ 2 r ~ . /.6
22
Suitable amphoteric surfactants for use herein include the amine oxide surfactants and
the alkyl ~ ' ' ylic acids.
A suitable example of an alkyl ~I-~di~bu~ , acid for use herein is MiranolCrM)
C2M Conc. r ~ by Miranol, Inc., Dayton, NJ.
Amin~ 0x~ surfactan~
Amine oxides useful herein include those . ' having the formula
R3(oR4)XNO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
a~yla~ u~,lu~uyl and alkyl phenyl group, or mixtures thereof, containing from 8 to
26 carbon atoms, preferably 8 to ~8 carbon atoms; R4 is an alkylene or
hydroxyalkylene grûup containing from 2 to 3 carbon atoms, preferably 2 carbon
atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R5 is
an alkyl or hydyroxyallyl group containing from I to 3, preferably from 1 to 2
carbon atoms, or a pul~ oxide group containing from I to 3, preferable 1,
ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an
oxygen or nitrogen atom, to form a ring structure.
rrhese amine oxide surfactants in particular include Clo-C1g alkyl dimethyl amine
oxides and Cg-C1g alkoxy ethyl dil~ uA~t~l amine oxides. Examples of such
materials include di~ Ll~ul,~ylal~h~, oxide, di~ ' oxide, bis-(2-
l~d~uA~ yl)dod~' ' oxide, d;.l.~.l.yl~Odc~' oxide,
d;ylulJjlt~,tla~ ' oxide, ' ~ '' ' y' - oxide,
dùd~.~ hJ~ c ~ ide, cetyl d;.. ,~,h)' oxide, stearyl
~;,...,lh~' oxide, tallow .I;...~;h~' oxide and dimethyl-2-
uAyu~ ad~' oxide. Preferred are C1o-C1g alkyl dil.l~hJlal.l...., oxide, and
C10 18 acylamido alkyl di~ y' - oxide.
Zwi
Zw ' surfactants can also be ' - - r ' I into the detergent ~
hereof. These surfactants can be broadly described as derivatives of secondary and
tertiary amines, derivatives of l.~t~,.u~.,l;c secondary and tertiary amines, orderivatives of quatemary: quaternary 1 ' , ' ' or tertiary sulfonium
Wo9s/28468 2~ 8~3~ P~,1/~J.,._. ~.~6
23
Betaine and sultaine surfactants are exemplary ~wilt~.iùn;c surfactants for
use herein.
RPt~ine SUrf~t~.~t
The betaines useful herein are those ~ulllr _ ' having the formula
R(R')2N+R2COO- wherein R is a C6-Clg l~yJ~ yl group, preferably a C10-C16
alkyl group or C10 16 acylamido alkyl group, each Rl is typically Cl-C3 allcyl,
preferably methyl,m and R2 is a Cl-Cs l~ydluwbyl group, preferably a Cl-C3
alkylene group, more preferably a Cl-C2 aLkylene group. Examples of suitable
betaines include coconut a"y' ' r Jl~jld;,..~lh~l betaine; hexadecyl dimethyl
betaine; C12 14 acyl~.,.;duylu,uyl~ ; Cg 14 ~yl~ll;d~h~,~yldiethyl betaine;
4[C14 16 a~ yl~ y~ ,y ~] I~I~u~yl . C16-18
a~y~ ' " ' ylb~L.~., C12 16 a y , jl l~,L~." [C12-16
~I,y' ' y' '- " - ylb~ Ll~. Preferred betaines are C12 18 dimethyl-ammonio
hexanoate and the C10-l8 a,y' ' r ~ ~ (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
S~1t~ P surf~rt~ t
The sultaines useful herein are those: . ' having the formula
(R(RI)2N+R2S03- wherein R is a C6-cl8 l~ydlu~l/~l group, preferably a C10-C16
alkyl group, more preferably a C12-C13 alkyl group, each Rl is typically Cl-C3
alkyl, preferably methyl, and R2 is a Cl-C6 I~.rdlU~UlJy; group, preferably a Cl-C3
alkylene or, preferably, h.~dlu~J~l~yk,..., group.
Anl~holytic ~ rt~n~
Ampholytic surfactants can be ;...,ull ' into the detergent ~ herein.
These surfactants can be broadly described as aliphatic derivatives of secondary or
tertiary amines, or aliphatic derivatives of k~,t~,~u~,l;c secondary and tertiary amines
in which the aliphatic radical can be straight chain or branched.
('~tinnir 5 '-
Cationic surfactants can also be used in the detergent ~ herein. Suitable
cationic surfactants include the quaternary ammonium surfactants selected from mono
WO 95/28468 2 1 8 7 3 ~ 2 PCI/US95103726
24
C6-C16, preferably C6-CIo N-alkyl or alkenyl a surfactants wherein theremaining N positions are substituted by methyl, I~ u~ .yl or Il.Yd~ P.~L
groups.
p~r~ y soluble or incn~ P h~ Pr ~ ~
The detergent . of the present invention may contain a partially Nluble or
insoluble builder compound, typically present at a level of from 1% to 80% by
weight, preferably from 10% to 70% by weight, most preferably from 20% to 60%
weight of the
Examples of partially water solub~e builders include the crystalline laye}ed silicates.
Examples of largely water insoluble builders include the sodium ~ nii1
Crystalline layered sodium silicates have the general formula
NaMSix02x+l YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514 and methods for their ~.. . p ~ ... are disclosed in DE-A-3417049 and DE-
A-3742043. For the purpose of the present invention, x in the general formula above
has a value of 2, 3 or 4 and is preferably 2. The most preferred material is ~-
Na2Si20s, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in granular
detergent "--~ as a particulate in intimate admixture with a solid, water-
soluble ionisable material. The solid, water-soluble ionisable material is selected
from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable -' ' zeolites have the unit cell formula Naz[(AlO2)z(SiO2)y].
XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and
x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The~1 ' material are in hydrated form and are preferably crystalline,
containing from 10% to 28%, more preferably from 18% to 22% water in bound
form.
W09s/28468 ~ 218~3~2 ~ 6
2~
The ~ lir~ ion exchange materials can be naturally occurring materials, but
are preferably synthetically derived. Synthetic crystalline ~ Cil ion exchange
materials are available under the ~ Zeolite A, Zeolite B, Zeolite P, Zeolite
X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula
Na 12 [A1O2) 12 (SiO2)12]- xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86
[(A1o2)g6(sio2)l06]- 276 H2O.
Ore~nic peroxyacid bleachin~ system
An essential feature of the invention is an organic peroxyacid bleaching system. In
one preferred execution the bleaching system contains a hydrogen peroxide source and
an organic peroxyacid bleach precursor compound. The production of the organic
peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate
bleaches. In an alternative preferred execution a preformed organic peroxyacid is
ln~,ulr ' directly into the ~ . C~ containing mixtures of a
hydrogen peroxide source and organic peroxyacid precursor in ~. ,l.;. -~;.... with a
preformed organic peroxyacid are also envisaged.
The organic peroxyacid bleaching system is preferably also provided with means for
delaying its release to the wash solution, such that in the T50 test method, the time
taken to achieve a ~ ;"" that is 50% of the ultimate ~ of the
peroxyacid bleach is more that 180 seconds, preferably more than 240 seconds. Any
of the means herein described for achieving the delayed release can be employed.Such delayed release has been found to be beneficial in helping to prevent 'patchy'
colour fading of fabrics in the wash.
~erhydrate bleaches
Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts
are normally I ' in the form of the alkali metal, preferably sodium salt at a
level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and
most preferably from 5 % to 25 % by weight of the,
WO 95128468 2 1 8 7 3 ~ P~,l/l . /L6
26
Examples of suitable inorganic perhydrate salts include per~orate, ~l~
P~ l ' , persulfate and persilicate salts and any mixtures thereof. l he inorganic
perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may
be included as the crystalline solid without additional protection. For certain
perhydrate salts however, the preferred executions of such granular ù~
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 I~u~JllJd~ of nominal formula
NaB02H202 or the t~ NaB2H22-3H2-
Alkali metal ~ ~L I ly sodium p~ are preferred~I-.y~ for inclusion in f~ in accordance with the invention.
r....~ containing ~ have been found to have a reduced tendency to
form l. `;.~l,1; gels in the presence of surfactants and water than similar
C~ which contain perborate. It is believed that this is because typically
~.~Lu..dt~, has a lower surface area and lower porosity than perborate ' ~,'
This low surface area and low porosity acts to prevent the co-gelling with fine
particles of surfactant ~ ~' and is therefore not ~ ' to dispensing.
Sodium p~ is an addition compound having a formula . ~ to
2Na2C03.3H202, and is available . ;..lly as a crystalline solid. The
~I,,arl~ is most preferably r ' ~ into such ~ in a coated form
which provides in product stability.
A suitable coating material providing in product stability comprises mixed salt of a
water soluble alkali metal sulphate and carbonate. Such coatings together with
coating processes have previously been described in GB-1,466,799, granted to Interox
on 9th March 1977. The weight ratio of the mixed salt coating material to
pf ~ lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to I
: 9, and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of
sodium sulphate and sodium carbonate which has the general formula
Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1 0 and
most preferably n is from 0.2 to 0.5.
wo ssl2s4~s 2 ~ ~ ~ 3 ~ 2 r~ 6
27
Other coatings which contain silicate (alone or with borate salts or boric acids or other
inorganics), waxes, oils, fatty soaps can also be used av~ y within the
present invention.
Potassium p~lUA.y r ' is another inorganic perhydrate salt of use in the
detergent C~ Ja.~ herein.
Perox~ ri~l bleach ~ r~r
Peroxyacid bleach precursors are r- ' which react with hydrogen peroxide in a
p~lh~d~ul~ reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be ,q~. - tr l as
o
X-C-L
where L is a leaving group and X is essentially any r" ~ y, such that on
Jlulv.~ the structure of the peroxyacid produced is
o
X-C -OOH
Peroxyacid bleach precursor . , ' are preferably i~ t' 1 at a level of from
0.5% to 20% by weight, more preferably from 1% to 15% by weight, most
preferably from 1.5% to 10% by weight of the detergent A '
Suitable peroxyacid bleach precursor -----r ' typically contain one or more N- or
O-acyl groups, which precursors can be selected from a wide range of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of
imidazoles and oximes. Examples of useful materials witbin these classes are
disclosed in G8-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,1147871, 2143231 and EP-A-0170386.
The Applicants have found that 'patchy' damage can be I : ' 'y associated with
peroxyacid bleach precursor . ' which on ~.I.~d-ul~ provides a
peroxyacid which is
woss/2s46s 2 1 ~ 7~ S/~ 6
28
(i) a perbenzoic acid, or non-cationic substituted derivative thereof; or
(ii) a cationic peroxyacid.
r precursors have also been found to be ~u~i~,ul~uly susceptible to the
problem.
Leavine erou~s
The leaving group, hereinafter L group, must be sufficiently reactive for the
p~,lh.~dlul~ reaction to occur within the optimum time frame (e.g., a wash cycle).
However, if L is too reactive, this activator will be difficult to stabilize for use in a
bleaching ~
Preferred L groups are selected from the group consisting of:
--0~ , --O~Y , and --0~
--N--C--R1 --N N --N_ 8_ _ R4
R3 L=l ' I C CH
y
R3 Y
-O--C H=C--C H=C H2 --O--C H=C--C H=C H2
-~C--R1 CH2_4 Y
O O
woss/2s46s ~ ~ 87~Q2 P~ 6
29
R3 0 Y
--0--C=CHR4, and --N--S--CH--R4
R3 0
and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from I
to 14 carbon atoms, R3 is an alkyl chain containing from I to 8 carbon atoms, R4 is
H or R3, and Y is H or a ~ h;l;~ , group. Any of Rl, R3 and R4 may be
substituted by essentially any functional group including, for example al~yl, hydroxy,
alkoxy, halogen, amine, nitrosyl, amide and ~ or alkyl: groups
The preferred <~ c, groups are -SO3 M+, -CO2 M+, -SO4 M+
-N+(R3)4X and O< N(R3)3 and most preferably -S03 M+ and -C02 M+
wherein R is an alkyl chain containing from I to 4 carbon atoms, M is a cation
which provides solubility to the bleach activator and X is an anion which provides
solubility to the bleach activator. Preferably, M is an alkali metal, or
substituted _ cation, with sodium and potassium being most preferred, and
X is a halide, hydroxide, ~. r ' or acetate anion.
Perbenzoic ~ri~i and deriv~ives ~h~reof DrecursorS
Perbenzoic acid precursor c~ u 1~ provide perbenzoic acid on pe.l..~.l.ul~
uitable O-acylated perbenwic acid precursor . ' include the substituted and
' benzoyl u-~yl,~ , sulfonates, including for example benzoyl
U~y~.,.l~..~ sulfonate:
o
~o~S03-
Also suitable are the b~ Lu.yl~l~iull products of sorbitol, glucose, and all ~ ri~Pc
with b~,Lu~laLil~g agents, including for example:
WO 95/28468 ~ P~
~873
OAc
AcO ~O
~,OAc
OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor , ' of the imide type include N-benzoyl
', t~ LU~I ethylene diamine and the N-benzoyl substituted ureas.
Suitable imidazole type perbenwic acid precursors include N-benzoyl imidazole and
N-benzoyl ' ' '- and other useful N-acyl group-cont~ining perbenzoic acid
precursors include N-benzoyl ~-uli~un~, dibenzoyl taurine and benzoyl
,,' acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl
tetraacyl peroxides, and the compound having the formula:
O O
[~40' O~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
~0
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
O
O C--CH2--CH2
CH2~cH2 ]n
w0 95/28468 2 ~ ~ 7 3 ~ 2 r~l,u~ 1~6
31
wherem n is from 0 to 8, preferably from 0 to 2, and R6 is an aryl, alkoxyaryl or
alkaryl group containing from 1 to 12 carbon atoms, or a substituted phenyl group
containing from 6 to 18 carbon atoms, preferably a benzoyl group.
Per~n7~ acid deriv~rive Drecursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
p~.h.~.l.ul~
Suitable substituted perbenzoic acid derivative precursors include any of the herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially any non-positively charged (ie; non-cationic) functional group including,
for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
A preferred class of substituted perbenzoic acid precursor: , ' are the amide
substituted . ' of the following general formulae:
R1--C--N--R2--C--L R1--N--C--R2--C--L
O R5 0 or R5 0 0
wherein Rl is an aryl or aLI~aryl group with from I to 14 carbon atoms, R2 is anarylene, or alkarylene group containing from I to 14 carbûn atoms, and R5 is H or an
alkyl, aryl, or alkaryl group containing I to 10 carbon atoms and L can be essentially
any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from 4 to 8 carbon atoms. R1 may be aryl, substituted aryl or alkylarylcontaining branching, or both and may be sourced from either synthetic
sources or natural sources including for example, tallow fat. Analogous structural
variations are I - ' for R2. The can include alkyl, aryl, halogen,
rlitrogen, sulphur and other typical substituent groups or organic . R5 is
preferably H or methyl. R1 and R5 should not contain more than 18 carbon atoms in
total. Amide substituted bleach activator . , of this type are described in EP-
A~170386.
('~rjnr~ yeroxyacid precursors
Woss/28468 2~3~ ' ,.c6
32
Cationic peroxyacid precursor f . ' produce cationic p~.u,.~.c;.is on
~ y~
Typirally, cationic peroxyacid precursfJrs are formed by ~ the peroxyacid
part of a suitable peroxyacid precursor rompound with a positively charged functional
group, such as an: or allyl ~ group, preferably an ethyl or
methyl group. Cationic peroxyacid precursors are typirally present in the
solid detergent rfm~ nC as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as described
llc~;.~ =. Alternatively, the peroxyacid precursor compound may be an alkyl
p~,.~bu~.yl;c acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK Patent
Application No. 9407944.9 and US Patent Appliration Nos. 08/298903, 081298650,
08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or alkyl
substituted alkyl or benwyl u.~y~ sulfonates, N-acylated
~-r- l; ' , and ' .~ t~l glucose benzoyl peroxides.
A preferred cationically substituted benzoyl u,..~ sulfonate is the 4-(trimethyl- ) methyl derivative of benzoyl ~ yl,~.. ~.. , sulfonate:
o
l~o~SO3-
Woss/284 21 ~7~
68 ~ P~~ 726
A preferred cationically substituted alkyl UA~b.,llL~,Il., sulfonate has the formula:
~ N ~1~ o /~
Preferred cationic peroxyacid precursors of the N-acylated ~,u~ ,Lolll class include
the trialkyl ammonium methylene benzoyl ~l~ ' , pcuLi~u~ trimethyl
methylene benzoyl ~.-, '
--N ' `~
Other preferred cationic peroxyacid precursors of the N-acylated ~ula~L~ l classinclude the trialkyl methylene alkyl ~ -, '
O O
)lNJ~
~+~(CH2)n ~)
where n is from O to 12.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl: )
ethyl sodium 4- ~l ' .' .r; carbonate chloride.
Alkyl ~I~U.~IiC acid bleach vrecursors
Allyl ~l~ubu~l;c acid bleach precursors form ~,~ubu~.~lic acids on p~ d-ulJa;a.
Preferred precursors of this type provide peracetic acid on ~ rdlul~a;a.
Preferred alkyl ~l~ubuA~ , precursor ~-----r- ' of the imide type include the N-,N,NINI tetra acetylated alkylene diamines wherein the alkylene group contains from
wo ss/2s46s 2 ~ ~ ~ 3 ~ ~ p~ 6
34 ~
I to 6 carbon atoms, I~u~i,ul~uly those . , ' in which the alkylene group
contains 1, 2 and 6 carbon atoms. T~LI~elyl~lly~ .; (rAED) is
preferred.
Other preferred alkyl ~I~I.UAylic acid precursors include sodium 3,5,5-tri-methyl
A~IU~IUAYb~ sulfonate (iso-NOBS), sodium no.~uyluA~ sulfonate
(NOBS), sodium a~.,tuAyl,~.~..~, sulfonate (ABS) and pentaacetyl glucose.
w095/28~68 ~1 873~2 P~ 6
3s
,~mi~lP substituted alkyl peroxyacid ~recursors
Amide substituted alkyl peroxyacid precursor f" 'I'~J'`'''I` are also suitable, including
those of the following general formulae:
R1--C--N--R2--C--L R1--N--C--R2--C--
Il 1 11 ~ 11 11
O R5 0 or R5 0 0
wherein Rl is an alkyl group with from I to 14 carbon atoms, R2 is an alkylene
group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group
containing I to 10 carbon atoms and L can be essentially any leaving group. Rl
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8
carbon atoms. R1 may be straight chain or branched alkyl containing branching,
or both and may be sourced from either synthetic sources or natural
sources including for example, tallow fat. Analogous structural variations are
' '- for R2. The ~ can include alkyl, halogen, nitrogen, sulphur
and other typical substituent groups or organic . RS is preferably H or
methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide
substituted bleach activator ~ - r - ' of this type are described in EP-A-0170386.
p~Pn7n-~7irl 1 peroxyacid vr~llr~nrc
Also suitable are precursor ~ , ' of the benzoxa~in-type, as disclosed for
example in EP-A-332,294 and EP-A-482,807, ~ ulcul~ those having the formula:
~N~C R,
wo gs/2s46s ~ 73 ~ 6
36
including tie substituted b ~ c of the type
R4~
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5may be the same or different ' selected from H, halogen, allyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an allcylgroup) and carbonyl functions.
An espPcially preferred precursor of the L type is:
1l
[~"C~
Prefonnp~ per~Yyacid
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid, typically at a level of from 1% to 15% by weight, more
preferably from 1% to 10% by weight of tbe .
preferred class of organic peroxyacid . ' are the amide substituted
of the following general formulae:
R1--C--N--R2--C--OOH R1--N--C--R2_ _ H
Il I 11 9 oo
O R5 0 orR5 0 0
wherein R1 is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is
an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and
RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carborl atoms. R1
WO 95/28468 ~ ~ ~3 7 3 ~ 2 P~ A /.c6
37
preferably contains from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8
carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or
alkylaryl containing branching, ~-~h~ ;n~, or both and may be sourced from either
synthetic sources or natural sources including for example, tallow fat. Analogous
structural variations are p, ' '- for R2. The can include alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon
atoms in total. Amide substituted organic peroxyacid ~ , ' of this type are
described in EP-A-0170386.
Other organic l.. ,uA~cids include diacyl and L~ JI~ UAid~ especiallyd;~.luAy; ~ ' acid,di~hluA~L ~ acidand
d;~,uAyh .~ C acid. Mono- and ~ acid, mono- and d;~,l,l~rlic
acid and N-~ lJ- ' ~ " U;C acid are also suitable herein.
nrin~o hl~rh
The: , herein are preferably free of chlorine bleach.
Rl.~ h ~lyst
The invention also . ~ . containing a catalytically effective
amount of a bleach catalyst such as a water-soluble manganese salt.
The bleach catalyst is used in a catalytically effectiYe amount in the,herein. By "catalytically effective amount" is meant an amount which is sufficient,
under whatever . u...~ .Li~ test condi~ions are employed, to enhance bleaching and
removal of the stain or stains of interest from the target substrate. Tbus, in a fabric
laundering operation, the target substrate will typically be a fabric stained with, for
example, various food stains. For automatic ' ' .. ' _ the target substrate may
be, for example, a porcelain cup or plate with tea stain or a ~I~.,~I.;I~n~ plate stained
with tomato soup. The test conditions will vary, depending on the type of washing
appliance used and the habits of the user. Thus, front-loading laundry washing
machines of the type employed in Europe generally use less water and higher
detergent r. ..\~. .,I.,.I;.~.~C than do top-loading U.S.-style machines. Some machines
have cv ~ .lr longer wash cycles than others. Some users elect to use very hot
water; others use warm or even cold water in fabric laundering operations. Of
_ _ . .
wossQ846s 21 87302 Y~/u~ . /,6
ourse~ the catalytic ~lru~ of the bleach catalyst will be affected by such
and the levels of b~each catalyst used in fully-formulated detergent and
bleach ~u., ~ can be d~ / adjusted. As a practical matter, and not by
way of limitation, the ~ and processes herein can be adjusted to provide
on the order of at least one part per ten million of the active bleach catalyst species in
the aqueous washing liquor, and will preferably provide from about I ppm to about
200 ppm o~ the catalyst species in the laundry liquor. To illustrate this point further,
on the order of 3 ~ u.~uku manganese catalyst is effective at 40C, pH 10 under
European conditions using perborate and a bleach precursor (e.g., benzoyl
~lukl~,Lal-l). An increase in . of 3-5 fold may be required under U.S.
conditions to achieve the same results. Conversely, use of a bleach precusor and the
manganese catalyst with perborate may allow the formulator to achieve equivalentbleaching at lower perborate usage ~evels than products without the manganese
catalyst.
The bleach catalyst mate~ial herein can comprise the free acid or be in the form of any
suitable salts.
One type of bleach catalyst is a catalyst system comprising a heavy metal cation of
defined bleach catalytic activity, such as copper, iron or manganese cations, anau~iliary metal cation having little or no bleach catalytic activity, such as zinc or
aluminum cations, and a sequestrant having defined stability constants for the catalytic
and auxiliary metal catiosls, I ' 'y c;lll~' ' - acid,
~Lil~ i - t~ Li.J' , ' , ' acid) and water-soluble salts thereof. Such
catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the ~ -based complexes disclosed in
U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts
include MnlV2(u-0)3(1,4,7-trimethyl-1,4,7-L,i~, ' ,2 (PF6)2, MnlI12(u-
O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-L~ ,yl~ )2 (ClO4)27 MnIV4(u-
0)6(1,4,7-LIi~y~ '< )4-(C104)2, MnIIIMnlV4(u-O)I(u-OAc)2 (1,4,7-
trimethyl-1,4,` ~ui~ ,lo..~n~.,)2-(ClO4)3, and mixtures thereof. Others are
described in European patent application publication no. 549,272. Other ligands
suitable for use herein include 1,5,9-trimethyl-1,5,9-L~ ' , 2-methyl-
1,4,7-hi~ lonul-an~, 2-methyl-1,4,7-LI;~, ' 1,2,4,7 t~Ll~ Lllyl-
1,4,7-Lli~."~l ' and mixtures thereof.
wo 95/28468 2 ~ ~ ~ 3 ~ ~ P~ I, 1, . . ~726
.
39
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, .- -. -1.~, manganese (IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-~.iaLa~"y- 1.,---, - ~ )(OCH3)3 (PF6). Still
another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble
complex of manganese (II), (III), and/or (IV) with a ligand which is a non-
~IJU~ .~ yvlyllyllu~.y compound having at least three l,o~l t~u~iv~ C-OH groups.Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, . c.~ i'ul, meso-inositol, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transitionmetals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands are of the formula:
R2 R3
R1 -N=l-B-l=N-R4
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl
groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six
ring. Said ring can further be C~hctit~ltfYl B is a bridging group selected from O, S.
CRSR6, NR7 and C=O, wherein R5, R6, and R7 can each be H, aLkyl, or aryl
groups, including substituted or I ' ' ' groups. Preferred ligands include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with ~ such as aLtcyl, aryl, alkoxy,
halide, and nitro. Pa~ ,ulall~ preferred is the ligand 2,2'-l,;~ ' Preferred
bleach catalysts include Co, Cu, Mn, Fe,-l,;a~,y-iJ~ and -b;it~J~Iid~lall.;....
~n~r~ c Highly preferred catalysts include Co(2,2'-~ 1;d~lall.;ll~)CI2.
Di(iavll~ )b;t~yl;~lylal--;l.c cobalt (II), Il;ad;~ y' cobalt(II)
perchlorate, Co(2,2-l,;*,J.id~ )202C104, Bis-(2,2'-b;a~y~id~ ) copper(lI)
, tris(di-2-~.;d~' ' ) iron(II) ~., ' ' , and mixtures thereof.
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including
N4Mnm(u-0)2MnIVN4)+and [Bipy2MnIU(u-0)2MnIVbipy2]-(Cl04)3.
The bleach catalysts may also be prepared by combining a water-soluble ligand with a
water-soluble manganese salt in aqueous media and . ~ the resulting
W09~128468 7 ~ ~73~2 ~ 726
mixture by C~a~l~LiOl~. Any convenient water-soluble salt of manganese can be used
herein. ~ ' ~ (II), (III), (IV) and/or (V) is readily available on a ~on rnPrci~l
scale. In some instances, sufficient manganese may be present in the wash liquor,
but, in general, it is preferred to add Mn cations in the ~ to ensure its
presence in catalytically-effective amounts. Thus, the sodium salt of the ligand and a
member selected from the group consisting of MnS04, Mn(C104)2 or MnC12 (least
preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range of
about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-
.~t~ by boiling and cooled by sparging with nitrogen. The resulting solution isevaporated (under N2, if desired) and the resulting solids are used in the bleaching
and detergent, . herein without further ~ . i ri. ,~
In an alternate mode, a water-soluble manganese source, such as MnSO4, is added to
the bleach/cleaning , or to the aqueous bleaching/cleaning bath which
comprises the ligand. Some type of complex is apparently formed in situ, and
improved bleach ~ r is secured. In such an in situ process, it is convenient
to use a, ' ' ' rnolar excess of t~.e ligand over the ~ and mole ratios
of ligand:Mn typically are 3:1 to 15:1. The additional ligand also serves to scavenge
vagrant metal ions such as iron fnd copper, thereby protecting the bleach from
", One possible such system is described in European patent ArF~ Dtinn
publication no. 549,271.
While the structures of some of the bleach-cataly~ing ~ , ' described
herein have not been elucidated, it may be speculated that they comprise chelates or
other hydrated ccnJl~' complexes which result from the interaction of the
carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the
oxidation state of the manganese cation during the catalytic process is not known with
cert..inty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to the
ligands' possible six points of attachment to the manganese cation, it may be
reasonably speculated th~t ..J~I~ species and/or "cage" structures may exist in
the aqueous bleaching media. Whatever the form of the active Mnligand species
which actually exists, it functions in an apparently catalytic manner to provideimproved bleaching ~ r~ on s~ubborn stains such as tea, ketchup, coffee,
blood, and the like.
Other bleach catalysts are described, for example, in ~uropean patent ~rplil~ti~n
publication no. 408,131 (cobalt complex catalysts), Europefn patent A~
W0 95128468 2 1 ~ 7 3 ~3~ r~ 6
41
ublication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455
ligand catalyst), U.S. 4,711,748 and European patent
application, publication no. æ4,952, (absorbed manganese on ~1 '
catalyst), U.S. 4,601,845 (, ' l support with manganese and zinc or
salt), U.S. 4,626,373 ( v 'ligand catalyst), U.S. 4,119,557 (ferric
complex catalyst), German Pat. ~ - 2,054,019 (cobalt chelant catalyst)
Canadian 866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants with
manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese
gluconate catalysts).
OrP~nir ~olymeric compound
Organic polymeric compounds are ~ Ul~Uly preferred - -r ' of the detergent
;.. . in accord with the invention. By organic polymeric compound it is
meant essentially any polymeric organic compound commonly used as ..'
and anti~ and soil suspension agents in detergent ~ -
Organic polymeric compound is typically ;..cull ' in the detergent ~)A.~ A~oftheinventionataleveloffromO.1%to30%,preferablyfromO.5%tolS%,most
preferably from 1% to 10% by weight of the
Examples of organic polymeric; . ' include the water soluble organic homo-
or co-polymeric ~Iy~u~u~ylil acids or their salts in which the puly~ubu~ylic acid
comprises at least two carboxyl radicals separated from each other by not more than
two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are ~UIy1. Ly' of MWt 2000-5000 and their culJuly
with maleic anhydride, such col uly...v. having a molecular weight of from 20,000 to
100,000, especially 40,000 to 80,û00.
Other suitable organic polymeric c- . ~ . ' include the polymers of acrylamide and
acrylate having a molecular weight of from 3,000 to 100,000, and the
~ ly' 'ru-., u .~ I u~lylll l having a molecular weight of from 2,000 to 80,000.
The polyamino I . ' are useful herein including those derived from aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
w0 95128468 ~ 2 ~ ~ 7 ~ ~ 2 ~ 6
42 !~
Terpolymers containing monomer units selected from maleic acid, acrylic acid,
~I~GalJ~uLi~ acid and vinyl alcohol, JJ~ ul~uly those having an average molecular
weight of from 5,0û0 to 10,û00 are also suitable herein.
ther organic polymeric r ' suitable for; . ~..Iu.,..li.... in the detergent
herein include cellulose derivatives such as methylcellulose,
~u~ ~ and l.ydlu~ ,.,llulose.
Further useful organic polymeric ~ 1 u ~c are the ~ ul.~ rl...c glycols, ~uL~,u;ally
those of molecular weight 1000-100û0, m~re ~ 20û0 to 8000 and most
preferably about 4000.
r ime Sn~ rli~ nt cornpound
The ~ ;. . - of the invention may contain a lime soap dispersant compound,
which has a lime soap dispersing power (LSDP), as defined hereinafter of no morethan 8, preferably no more than 7, most preferably no more than 6. The lime soapdispersant compound is preferably present at a level of from 0.1% to 4û% by weight,
more preferably 1% to 2û% by weight, most preferably from 2% to lû% by weight
of the C~ N~
lime soap dispersant is a material that prevents the ~ ;UII ûf all~li metal,
or amine salts of fatty acids by calcium or magnesium ions. A numerical
measure of the crf~t;~ a of a lime soap dispersant is given by the lime soap
dispersing power (LSDP) which is determined using the lime soap dispersion test as
described in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem.
Soc., volume 27, pages ~8-90, (1950). This lime soap dispersion test method is
widely used by ~ in this art field being referred to, for example, in the
following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3;
W.N. Linfield, Tenside Surf. Det., Volume 27, pageslS9-161, (199û); and M.K.
Nagarajan, W.F. Masler, Cosmetic3 and Toiletries, Volume 104, pages 71-73,
(1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate
required to disperse the lime soap deposits formed by û.û25g of sodium oleate in30ml of water of 333ppm CaCO3 (Ca:~g=3:2) equivalent hardness.
Surfactants having good lime soap dispe~sant capability will include certain amine
oxides, betaines, ' ~ ' , alkyl C:LLW~ ' ' ' and .~hU~ ' ' ' alcohols.
W095/28468 2~ ~7~ r~ 6
43
Exemplary surfactants having a LSDP of no more than 8 for use in accord with theinvention include C16-CIg dimethyl amine oxide, C12-C1g alkyl ~:lhvAy '~ with
an average degree of ~ uA~l~Lion of from 1-5, l~uLi~uLuly C12-C1s alkyl
UA~ '' surfactdnt with a degree ûf ~IIUAyl~Liul~ ûf abûut 3 (LSDP=4), and the
C13-C1s ~LI~OAY~ ' alcohols with an average degree of ~LIIuAyldLiù.l of either 12
(LSDP=6) or 30, sûld under the trade names Lutensol A012 and Lutensol A030
l~Li~,ly, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the article by
M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume
104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants include
certain water-soluble salts of copul~".~.~ of acrylic acid, ~ acid or mixtures
thereof, and an acrylamide or substituted acrylamide, where such polymers typically
have a molecular weight of from 5,000 to 20,000.
Suds ~ system
The detergent ~ of the invention, when formulated for use in machine
washing ~ , , preferably comprise a suds ~ . system present at a
level of from û.û1% to 15%, preferably from O.û5% to lû%, most preferably f}om
0.1% to 5% by weight of the ...., ,..-~:1;....
Suitable suds ~ g systems for use herein may comprise essentially any known
antifoam compound, including, for example silicone antifoam, , ' 2-alkyl and
alcanol antifoam .
By antifoam compound it is meant herein any compound or mixtures of
which act such as to depress the foaming or sudsing produced by a solution of a
detergent ~ u i ' ~y in the presence of agitation of that solution.
P~uLi.,ul~ul~ preferred antifoam ~ for use herein are silicone antifoam . ' defined herein as any antifoam compound including a silicone
Such silicone antifoam l-----r - ~ also typically contain a silica . The
term "silicone~ as used herein, and in general throughout the industry, f ~ a
variety of relatively high molecular weight polymers containing siloxane units and
U~U~JI group of various types. Preferred silicone antifoam ~, ,1~ ", 1~ are the
wo ss/2s468 2 1 8 7 31~ 6
44
siloxanes, ydl~iuul~uly the ~OIyJi~ yl~iluA~.~ having ~ ;lyl end blocking
units.
Other suitable antifoam ~ ' include the ' ~lic fatty acids and soluble
salts thereof. Tbese materials are described in US Patent 2,954,347, issued
September 27, 1960 to Wayne St. John. The .~ ;;c fatty acids, and salts
thereof, for use as suds suppressor typically have hJIIu~ubyl chains of 10 to about 24
carbon atoms, preferably 12 to 18 carbon atoms. Suitable salt~i include the alkali
metal salts such as sodium, potassium, and lithium salts, and ~mm~tnil~m and
salts.
Other suitable imtifoam ~ include, for example, high molecular weight fatty
esters (e.g. fatty acid l.i~ .i~s), fatty acid esters of ,v ' alcohols, aliphatic
Clg-C40 ketones (e.g. stearone) N-alk!tlated amino tria~ines such as tri- to hexa-
al~ or di- to tetra alk~ . hl .. l, ;- ~;- -- . formed as products of
cyanuric chloride with two or three moles of a primary or secondary amine conti~ining
I to 24 carbon atoms, propylene oxide, bis stearic acid amide and l~u~ ~u ~l di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
Copolymers of dhylene oxide and pro"lene oxide, ~ the mixed
:tlluA~ kJt~JluyuA~ ' fatty alcohols with an alkyl chain length of from 10 to 16carbon atoms, a degree of ~lllUA~ LiUI~ of from 3 to 30 and a degree of ylUyUAJI~li
of from I to 10, are also suitable antifoam cr~m~ iC for use herein.
Suitable 2-alky-alcanols antifoam ~ , ' for use herein have been described in
DE 40 21265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to C16alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in
the a position by a Cl to Clo alkyl chain. Mixtures of 2-alkyl-alcanols can be used in
the ~ - according to the present invention.
A preferred suds . ~ e, system comprises
(a) antifoam compound, preferably silicone antifoam compound, most preferably a
silicone antifoam compound comprising in ! ' ' "
(i) yOlyd;lll.,lllyl siloxane, at a level of from 50% to 99%, preferaoly 75%
to 95% by weight of the silicone antifoam compound; and
Wo 95128468 2 ~ 8 7 :~ ~ 2 r~l~u~.. . A~726
4s
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight
of the silicone/silica antifoam compound;
wherein said silica/silicone antifoam compound is i..~u.~ ' at a level of
from 5% to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol rake
copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1% to 10% by weight; a ~KuL~,ul~uly preferred silicone glycol rake
copolymer of this type is DCO544, . 'Iy available from DOW
Corning under the tradename DCO544;
(c) an inert carrier fluid compound, most preferably comprising a C16-C18
~LIlu~.y' ' alcohol with a degree of clhu~yl~Lu~ of from S to 50, preferably 8
to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A preferred particulate suds suppressor system useful herein comprises a mixture of
an alkylated siloxane of the type .,.,., ~ disclosed and solid silica.
The solid silica can be a fumed silica, a l . ' silica or a silica, made by the gel
formation technique. The silica particles suitable have an average particle size of
from 0.1 to 50 I.~u....LI~, preferably from 1 to 20 u..~,L.~ and a surface area
of at least 50m2/g. These silica particles can be rendered llyJl~r- ' - by treating
them with dialkylsilyl groups and/or trialkylsilyl groups either bonded directly onto
the silica or by means of a silicone resin. It is preferred to employ a silica the
particles of which have been rendered l~,~J-u~JI-ùl ;-, with dimethyl and/or trimethyl
silyl groups. A preferred particulate antifoam compound for inclusion in the
detergent ~ in ~c~ with the invention suitably contain an amount of
silica such that the weight ratio of silica to silicone lies in the range from 1:100 to
3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds , r ~ system is ~ LJ by a l-~J-u~l-uL~;c
silanated (most preferably trimethyl-silanated) silica having a particle size in the range
from 10 . ~ to 20 ~ and a specific surface area above 50m2/g,
intimately admixed with dimethyl silicone fluid having a molecular weight in the
Woss/2s~6s 2~873a2 r~ 6
range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica
of from about 1:1 to about 1:2.
A highly preferred particulate suds a~ system is described in EP-A-0210731
and comprises a silicone antifoam compound and an organic carrier material having a
melting point in the ran~e 50C to 85C, wherein the organic carrier material
comprises a monoester of glycerol and a fatty acid having a carbon chain containing
from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds
' ~ r L~ systems wherein ~he organic carrier material is a fatty acid or alcoholhaving a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof,
with a melting point of from 45C to 80C.
Other highly preferred particulate suds ,~ systems are described in
copending European Application 91870007.1 in the name of the Procter and Gamble
Company which systems comprise silicone antifoam compound, a carrier material, an
organic coating material and glycerol at a weight ratio of glycerol: silicone antifoam
compound of 1:2 to 3:1. Copending European Application 91201342.0 also discloseshighly preferred particulate suds a ~ , systems comprising silicone antifoam
compound, a carrier material, an organic coating material and crystalline or
amorphous ' ' at a weight ratio of: ' : silicone antifoam
compound of 1:3 to 3:1. The preferred carrrier material in both of the above
described highly preferred granular suds controlling agents is starch.
An exemplary particulate suds ~ L~ , system for use herein is a particulate
~ ~. t, made by an ''LGI'''''' '~1;'''' process, comprising in
.. ..
(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in,
~Iy~" ' yl siloxane and silica;
(ii) from 50% to 90%, preferably from 60% to 80% by weight of the c~mrn~
of carrier material, preferably starch;
(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of
~g' binder compound, where herein such compound can be any
compound, or mixtures thereof typically employed as binders for
wo 9S/28468 ~ 6
2 1 ~373~)~
: ~ ~' , most preferably said ~ r . . ~-- binder compound comprises a
Cl6-C1g ~ u~.y' ' alcohol with a degree of c~l-u~ ,io" of from 50 to 100;
and
(iv) from 2% to 15%, preferably from 3% to 10%, by weight of C12-C22
~ d-~ ~, ' fatty acid.
Polymeric dye ' inhihirinF ;~,~ntc
The detergent ~ herein may also comprise from 0.01% to 10 %,
preferably from 0.05% to 0.5% by weight of pûlymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine
N-oxide polymers, Cu~vly~ of N-~;".YI~,J.-, ' ' and N~ ;~ul~"
~Iyvillylu.yllulidu.l~ polymers or ' thereûf.
~ Polyamine N-oxide Dolymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula:
p
(I) Ax
R
wherein P is a ool~ unit, whereto the R-N-O group can be attached to, or
wherein the R-N-O group forms part of the ~ul~ unit or a ~ n of
both.
00 0
Il 11 11
A is NC, CO, C, -O-, -S-, -N-; x is O or 1;
R are aliphatic, ~I,u~' ' aliphatics, aromatic, I..,t~,.u~ l;c or alicyclic groups or
any ' thereof whereto the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group is part of these groups.
WO 95/2N468 ~ 6
48
The N-O grrv~up can be IC~ ' ' by the following general structures:
O
1` o
(R1 ) X - I -(R2)Y l\
(R3)z or --N~R~ )x
wherein R1, R2, and R3 are aliphatic groups, aromatic, I~ ,lic or alicyclic
groups or .,~ hereof, x or/and y or/and z is 0 or I and wherein the
nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group
forms part of these groups. The N-O group can be part of the p~ lc unit (P)
or can be attached to the polymeric backbone or a, ' of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the p~.l~..._.i~l~
unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or k~ ,lic groups. One class of said polyamine N-oxides comprises the
group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the
R-group. Preferred polyamine N-oxides are those wherein R is a ~.~t~.~J~,lic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group is attached to the R-group.
Other suitahvle polyamine N-oxides are the polyamine oxides whereto the N-O group
is attached to the pfvl.~ ' ' unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having the
general formula a) wherein R is an ar~n~ .,L., or alicyclic groups wherein
the nitrogen of the N-0 functional group is part of said R group. Examples of these
classes are polyamine oxides wherein R is a ll~t~ y.,li~ compound such ilS pyrridine,
pyrrole, imidazole and derivatives thereof.
WO 95/28468 2 1 ~ 7 3 0 2 P~ 51~3726
49
Anotner preferred class of polyamine N-oxides are the polyamine oxides having the
general formula (I) wherein R are aromatic, h. L~u~ liC or alicyclic groups wherein
the nitrogen of the N-0 functional group is attached to said R groups. Examples of
these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed is
water-soluble and has dye transfer inhibiting properties. Examples of suitable
polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers,
polyamide, ~ul~ and mixtures tnereof.
The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide
groups present in tne polyamine oxide polymer can be varied by dlJ,ul~r
u u~ iun or by a,u,ul~ . degree of N-oxidation. Preferably, the ratio of
amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The polymers of the present
invention actually encompass random or block cu~ where one monomer type
is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa <
7, more preferred PKa < 6.
The polyamine oxides can be obtained in almost any degree of pUlJ~ iul~. The
degree of pul~ .;~Liu.. is not critical provided the material has the desired water-
solubility and .IJ~, ' . " ,, pûWer. Typically, the average molecular weight is
within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more
preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
b) Co~olyrn~ of N- ~ n.l N ~;IIJl; 1~,--1~
Preferred polymers for use herein may comprise a polymer sclected from N-
vi..yll~id~ul~ N-~ llulido..c ~u~ wherein said polymer has an average
molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000,
rnost preferably from 10,000 to 20,000. The preferred N-v;~ .;i~lc N-
Vi~ llUlidUllC UUIJUl,~ll~..l:l have a molar ratio of N-~ id~ul~ to N-
JJIlulidu~ from 1 to 0.2, more preferably from 0.8 to 0.3, most preferablyfrom 0.6 to 0.4 .
.
WO 95/28468 2 ~ 8 7 3 0 2 r ~l/o. /~6
C) ~olyv;-~ylyJ~
The detergent .~ h~rein may also utilize ~Iyv;~ylyylluli:lù..~, ("PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from 5,000
to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000to 15,000. Suitable polyv;~ yll, ' ' are ~ly vailable from ISP
Corporation, New York, NY and Montreal, Canada under the product names PVP K-
15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average
molecular weight of 360,000). PVP K-15 is also available from ISP Corporation.
Other suitable ~Iyvi..Jl~yllulidull.,~ which are "y available from BASF
ronp~nn include Sok~lan HP 165 and Sokalan HP 12.
r~ly v yl~ ' ' may be illWly~ ' ~ in the detergent ~ , herein at a
level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3%
by weight, and more preferably from 0.1% to 2% by weight. The amount of
~Iy v;~ yllulidu..~ delivered irl the wash solution is preferably from 0.5 ppm to 250
ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
d) POI~- n~
The detergent ..~ c herein may also utilize ~I ~ v J' '~ ' as
polymeric dye transfer inhibiting agents. Said pol~v~ yl~ have an average
molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more
preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.
The amount of ~ulyvillylc "' ;lI-,UI, ' ' in the detergent: . ~ may
be from 0.ûl % to 5 % by weight, preferably from 0.05 % to 3 % by weight, and more
preferably from 0.1% to 2 % by weight. The amount of ~ol~ v ;lly' ' ~ '
delivered in the wash solution is typically from 0.5 ppm to 250 ppm, preferably from
2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
e) r~ly~;..~l;.~;;i~ulc
The detergent ~ herein may also utiliæ pol~ v ;llyli~";d~ul~ as polymeric
dye transfer inhibiting agent. Said yuly Vll~y~ preferably have an average
wossr~s46s 2 ~ 87 302 r~ 6
51
molecular weight of from 2,500 to 400,00~, more preferably from 5,000 to 50,000,and most preferably from 5,000 to 15,000.
The amount of pol~d~ iu~ cu.~ u~t~i in the detergent: , may be
from 0.01% to 5% by weight, p~;eferably from 0.05% to 3% by weight, and mûre
preferably from 0.1% to 2% by weight. The amount of pul~villy" ' '- delivered
in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150
ppm, more preferably from S ppm to 10~ ppm.
Optical briehtener
The detergent ~ u~ herein may also optiona'lly contain from about 0.005% to
5% by weight of certain types of hydrophilic optical brighteners which a'lso provide a
dye transfer inhibition action. If used, the ~,,.,.1..,~;l;..,.~ herein will preferably
comprise from about 0.01% to 1% by weight of such optica~
The hydrophilic optical I ' useful in t'ne present invention are those having
the structural formula:
Rl Rl
N~ ~ lH E:~NH~N(~N
R2 SO3M SO3M Rl
wherein Rl is selected from anilino, N-2-bis-l.yJ.uA~ l and NH-2 h~Jlu,.~tllJl;
R2 is selected from N-2~ h~Jlu,.~ l, N 21,~d.UA~ I N
, ' ' o, chloro and amino; and M is a sa'lt-forming cation such as sodium or
potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-l,yJ.u,.~ l and M is a
cation such as sodium, the brightener is 4,4',-bis[(4-anilino-~(N-2-bis-ll~dlu7.~
s-triazine-2-yl)amino]-2,2'-~ r.. r acid and disodium salt. Tbis particular
brightener species is commercially marketed under the tradename Tinopai-UNF~A-GXby Ciba-Geigy Corporation. Tinopal-UN~'A-GX is tne preferred ;.~J.ulJl.i;;c optica
brightener useful in the detergent ~ , herein.
W0 95/28468 L ~ 2 r~ 0~726
52
When in the above formula, Rl is anilino, R2 is N-2-~JIu~ -N-2-
~and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-llydlu~ .LIl.~ N ~ L~ .) s triazine-2-yl)amino]2,2'-~filhPnPrli~lllf ~nir acid
disodium salt. This par~icular brightener species is .,;ally marketed under the
tradename Tinopal 5BM-GX by Ciba-Cieigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-
r,. acid, sodium salt. This particular brightener species is
CU...IG.,.. ;ally marketed under the tradename Tinopal AMS-GX by Ciba Geigy
~fj~n
The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition I ' benefits when used in
with the selected polymeric dye transfer inhibiting agents 1 . . . ~ r
described. The ' of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Ti~opal
5BM-GX and/or Tinopal AMS-GX) provides li" ' '~, better dye transfer
inhibition in aqueous wash solutions than does either of these two detergent
~ when used alone. Witbout being bound by theory, it is
believed that such brighteners work this way because they haYe high affinity forfabrics in the wash solution and therefore deposit relatively quick ~n these fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be defined
by a parameter called the ~exhaustion ~rr.~.~.... The exhaustion cwfficient is in
general as the ratio of a) the brightener material deposited on fabric to b) the initial
brightener . in the wash liquor. r _~ with relatively high
exhaustion ~ are the most suitable for inhibiting dye transfer in the context
of the present invention.
Of course, it will be ..~ ' that other, ;~"~. ' optical brightener types of
""~1~ ,1~ can optionally be used im the present . to provide ~u...~.,~,.al
fabric "~ ;l.t~ " benefits, rather than a true dye transfer inhibiting effect. Such
usage is ~,u.~v, I and well-known to detergent r~
Soffpnin~ 7~e~nf~
wo gs/28468 ~ 1~7 3 ~ 2 r~.,uv- 1~6
s3
Fabric softening agents can also be il~ u~l ' into laundry detergent ~ 1
in accordance with the present invention. These agents may be inorganic or organic
in type. Inorganic softening agents are . . ' ~ ' by the smectite clays disclosed in
GB-A-I 400 898. Organic fabric softening agents include the water insoluble tertiary
amines as disclosed in GB-A-1514 276 and EP-B-0 011 340.
Levels of smectite clay are normally in the range from 5% to 15%, more preferably
from 8% to 12% by weight, with the material being added as a dry mixed componenttrv~ the remainder of the ' ' Organic fabric softening agents such as the
water-insoluble tertiary amines or dilong chain amide materials are i ~ l at
levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the
high molecular weight yul~ oxide materiavs and the water soluble cationic
materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% byweight.
Other Optiona~ nt~
Other optional ingredients suitable for inclusion in the c-~ of the invention
include perfumes, colours and filler salts, with sodium sulfate being a preferred filler
salt.
Fl-rrn of the ~ul~
The detergent . of the invention can be formulated in any desirable form
such as powders, granulates, pastes, liquids and gels. Granular cc, .~ are
preferred.
The detergent ~ of the present invention may be formulated as liquid
detergent c.. ,l~ c Such liquid detergent ~,,., l,..~;l;.."~ typically comprise from
94% to 35% by weight, preferably from 90% to 40% by weight, most preferably
frorn 80% to 50% by weight of a liquid carrier, e.g., water, preferably a mixture of
water and organic solvent.
Gel "~ iliull~
WO 9~128468 ~ 6
~1 ~73Q~ ~
The detergent ~c ~ of the present invention may also be in the form of gels.
Such . . are typically formulated with polyakenyl polyether having a
molecular weight of from about 750,000 to about 4,000,000.
Solid ~
The detergent . of the invention are preferably in the form of solids, such
as powders and granules.
The particle size of the ~ . of granular ~ . in accordance with the
invention should preferably be such that no more that 5 % of particles are greater than
1 .4mm in diameter and not more than 5 % of pa~ticles are less than 0.15mm in
diameter.
The bulk density of granular detergent ~ in accordance with the presentinvention typically have a bulk density of at least 450 g/litre, more usually at least
600 g/litre and more preferably from 650 g/litre to 1200 g/litre.
Bulk density is measured by means of a simple fumnel and cup device consisting of a
conical furmel moulded rigidly on a base and provided with a flap valve at its lower
extremity to allow the contents of the funnel to be emptied into an axially aligned
cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at its
respective upper and lower ~'Yt~rr -i~'C It is mounte~ so that the lower extremity is
140 mm above the upper surface of the base. The cup has an overall height of 90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal
volume is 500 ml.
To carry out a t, the funnel is f lled with powder by hand pouring, theflap valve is opened and powder allowed to overfill the cup. The filled cup is
removed from the frame and eYcess powder removed from the cup by passing a
straight edged implement e.g. a knife, across its upper edge The filled cup is then
weighed and the value obtained for the weight of powder doubled to provide the bulk
density in g/litre. Replicate are made as required.
rocesses - eranular c .~ ~o~ s
W0 95~8468 2 1 ~ 7 3 0 2 ~ 6
.
ss
In general, granular detergent ~ in accordance with the present invention
can be made via a variety of methods including dry mixing, spray drying,
i.", and O
W~ m.~tl-~lc
The ~ O ~ ;; of the invention may be used in essentially any washing or cleaningmethod, including machine laundry and d;~h. ' _ methods.
r~ w~ method
A preferred machine d;~ , method comprises treating soiled articles selected
from crockery, glassware, lloll~ .. w~uc; and cutlery and mixtures thereof, with an
aqueous liquid having dissolved or dispensed therein an effective amount of a machine
d~ ;.Io ~ in accord with the inevntion. By an effective amount of the
machine .I;~hw ' ~ . . it is typically meant from 8g to oOg of product
dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical
product dosages and wash solution volumes commonly employed in Wll~
machine d;~ methods.
r ' ' ~ 1 'L methods
Machine laundry methods herein comprise treating soiled laundry with an aqueous
wash solution in a washing machine having dissolved or dispensed therein an effective
amount of a machine laundry detergent ~ :l;.." in accord with the invention. Thedetergent can be added to the wash solution either via the dispenser drawer of the
washing machine or by a dispensing device. By an effective amount of the detergent
it is typically meant from 40g to 300g of product dissolved or dispersed
in a wash solution of volume from S to oS litres, as are typical product dosages and
wash solution volumes commonly employed in w..~. ' machine laundry
methods.
In a preferred washing method herein a dispensing device containing an effectiveamount of detergent product is introduced into the drum of a, preferably front-
loading, washing machine before the ~ of the wash cycle.
W0 95/28468 2 7 ~ 7 3 1~ /.6
56
T}fe dispensing device is a container for the detergent product which is used to deliverthe product directly into the drum of the washing machine. Its volume capacity
should be such as to be able to contain sufficient detergent product as would normally
be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the: of
the wash cycle of the washing machine water is introduced into the drum and the
drum periodically rotates. The design of the disFfensing device should be such that it
permits: of the dry detergent product but then allows release of this
product during the wash cycle in response to its agitation as the drum rotates and also
as a result of its immersion in the wash water.
To allow for release of the detergent product during the wash the device may possess
a number of openings through which the product may pass. Alternatively, the device
may be made of a material which is permeable to liquid but l..~l~ to the solid
product, which will allow release of dissolved product. Preferably, the detergent
product will be rapidly released at the start of the wash cycle thereby providing
transient localised high ~ of ~ r ' such as water-soluble builder
and heavy metal ion secuestrant ...~ in the drum of the washing machine at
this stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way that
container integrity is maintained in both the dry state and during the wash cycle.
Especially preferred dispensing devices for use in accord with the invention have been
described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-
0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in
Chemist, November 1989, pages 41-46 also describes especially
preferred dispensing devices for use with granular laundry products which are of a
type commonly know as the "granulette".
Especially preferred dispensing devices are disclosed in European Patent Application
Publication Nos. 0343069 & 0343070. The latter Application discloses a device
comprising a flexible sheath in the form of a bag extending from a support ring
defining an orifice, the orifice being adapted to admit to the bag sufficient product for
one washing cycle in a washing process. A portion of the washing medium flows
through the orifice into the bag, dissolves the product, and the solution then passes
woss/28468 21 ~73t~2 r~l,u~ 6
57
outwardly through the orifice into the washing medium. The support ring is provided
with a masking r ~ ''''1 to prevent egress of wetted, ~ vl~, product, this
typically comprising radially extending walls extending from a central
boss in a spoked wheel c~ , or a similar structure in which the walls have a
helical form.
Pretreatment w~chir~ thful
In a ~ La~ wash method aspect of the invention a soiled/stained substrate is
treated with an effective amount of a IJlC~lCd~ solution containing a heavy metal
ion s~ 'c~nr, but no enzyme , The solution might optionally contain
other l.v.. ~ detergent ~ . such as 5~1rf~r~ c builders, and detergent
polymers Preferably the solution also contains water-soluble builder
The level of the heavy metal ion sequestrant in said ~--L c solution is typically
from 0 0005 % to 1%, and preferably is more than 0 05 % .
The ~JIL' ' ' solution is allowed to remain in contact with the soiled substrate for
an effective time interval. Said time interval will typically be from 10 seconds to
1800 seconds, more preferably from 60 seconds to 600 seconds.
The soiled substrate is then washed using a suitable washing method wherein an
enzyme-containing detergent product is employed The washing method may for
example, be any of the machine ' ' ... ' l" or machine laundry washing methods
described herein.
In the detergent ~ the dbbl~,~ia~ component i~ have the
following meanings:
XYAS : Sodium Clx - C1y alkyl sulf-dte
24EY : A C12 15 ~lCClc,,l.;lldll~l~ linearprimary alcohol
condensed with an average of Y moles of ethylene
oxide
woss/2s46s ~l 8~32 r~ 6
XYEZ A Clx - Cly ~JIalu~ ly linear primary alcûhol
condensed with an average of Z moles of ethylene
oxide
XYEZS : ClX - Cly sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
TFAA : C16-Clg alkyl N-methyl glucamide.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula o-Na2si25
Carbonate : Anhydrous sodium carbonate
r~ly~bu,~y~ : Copolymer of 1:4 1ll 'ci~ li., acid, average
molecular weight about 80,000
Zeolite A : Hydrated Sodium ~1 " of formula
Nal2(A102SiO2)12. 27H20 having a primary particle
size in the range from I to 10 Oll.~t~.
Citrate : Tri-sodium citrate dihydrate
r~.~; (fast release : Anhydrous sodium ~.~L bleach of empirical
particle) formula 2Na2C03.3H202 coated with a mixed salt of
formula Na2SO4.n.Na2CO3 where n is 0.29 and
where the weight ratio of ~., ~ to mixed salt is
39: 1
r~L (slow release : Anhydrous sodium I ' bleach coated with a
particle) coating of sodium silicate (Si2O:Na2O ratio = 2:1) at
a weight ratio of p~,...u. to sodium silicate of
39:1
TAED : Tc:~.~et~
W095J28468 21~73~ Pcr/US95/03726
o
sg
TAED (slow release : Particle formed by ~ cl ~ TAED with citric
particle) acid and IJul~ yl~ glycol (PEG) of Mw=4,000
with a weight ratio of . , of TAED:citric
acid:PEG of 75:10:15, coated with an external coating
of citric acid at a weight ratio of ~E,~' citric
acid coating of 95:5.
Benzoyl Caprolactam (slow : Particle formed by a~ ~ ~ benzoyl ~..'
release particle) (BzCI) with citric acid and pul~ .. glycol (PEG)
of Mw=4,000, with a weight ratio of . . ûf
BzCl:citric acid:PEG of 63:21:16, coated with an
external coating of citric acid at a weight ratio of
acid coating of 95:5
TAED (fast release : Particle formed by ~ In ~ L, TAED with partially
particle) neutralised ~I.~wbu~' at a ratio of
TAED.~ wb~ ~ of 93:7, coated with an
external coating of pol~u~' at a weight ratio of
a~ of 96:4
EDDS (fast release : Particle formed by spray-drying EDDS with MgSO4 at
particle) a weight ratio of 26:74
Protease : Proteolytic enzyme sold under the tradename Savinase
by Novo Industries A/S with an activity of 13
KNPU/g.
Protease (slow release : An enzyme prill containing proteolytic enzyme sold
particle) under the Tradename Savinase by Novo Industries A/S
with an activity of 13 KNPU/g coated with a coating
of sodium silicate (SiO2:Na2O ratio = 2:1) at a
coating level of 5%.
Amylase : Amylolytic enzyme sold under the tradename
Termamyl 60T by Novo Industries A/S with an activity
of 300 KNU/g.
W095/28468 ~ ' 2~ 87302 F~ .. IL6
Cellulase : Cellulosic enzyme sold by Novo Industries A/S with an
activity of 1000 CEV/g.
Lipase : Lipolytic enzyme sold under the tradename Lipolase by
Novo Industries A/S with an activity of 165 KLUlg
CMC : Sodium ~I.UA~ l cellulose
HEDP : ~ JlUA~ ' .' acid
EDDS : 11~ ' -N, N'- disuccinic acid, [S,S] isomer
in the form of the sodium salt.
PVNO : Poly (4-~ ' ) N oxide copolymer of
;J~ùl~, and ~ J,~ulidu~ having 4n average
molecular weight of 10,000.
Granular Suds Suppressor : 12% .~il- 'sili.,4, 18% stearyl alcohol,70% starch in granular form
Nonionic : C13-C15 mixed ~.u,.y' 'I~JIUIJU~.~' ' fatty
alcohol with an average degree of ~IhuA~14~iull of 3.8
and an average degree of ~IU~U~.~IdliU~. of 4.5 sold
under the tradename Plurafac LF404 by BASF Gmbh
(low foaming)
r ~ ' : Sodium mP~Cil (SiO2:Na2O ratio = 1.0)
Phosphate : Sodium ~ ,ol~
480N : Rdndom copolymer of 3:7 acrylic/-r.~.h4. lylic acid,
average molecular weight about 3,5ûO
PBl : Anydrous sodium perborate l.~o.. ul.. ~ - in
compactPd particulate form to retard reledse of
hydrogen peroxide
W0 9~128468 ~ 1 8 7 30 2 ~ '0 Z726
61
Cationic lactam : Cationic peroxyacid bleach precursor salt of trialkyl
z methylene Cs-alkyl ~ ' with
tosylate
DETPMP : Diethylene triamine penta (methylene ~I~.. ~L,II~,lli.,
acid), marketed by Monsanto under the tradename
Defzuest 2060
Bismuth nitrate : Bismuth nitrate salt
Paraffin : Paraffin oil sold under the tradename Winog 70 by
~J~. ' 'I
BSA : Amylolytic enzyme sold under the tradename LE17 by
Novo Industries A/S (approx 1% enzyme activity)
Sulphate : Anhydrous sodium sulphate.
pH : Measured as a 1% solution in distilled water at 20C.
~. ' 1
The following laundry detergent I . were preparecz, the values being
by weight of the f,~ A is a . ~.,
B to D ~re in accord with the invention:
A B C D
45AS/25AS (ratio = 3:1) 9.1 9.1 9.1 9.1
35AE3S 2.3 2.3 2.3 2.3
24E5 4.5 4.5 4.5 4.5
wo ss/2s468 2 1 8 7 3 ~ n6
62
TFAA2.0 2.0 2.0 2.0
Zeolite A 13.2 13.2 13.2 13.2
NaSKS-6/citric acid (79:21) 15.6 15.6 15.6 15.6
Carbonate 7.6 7.6 7.6 7.6
TAED (fast release particle) 6.3
TAED (slow release particle) - 5.0 - 2.3
Beruoyl Caprolactarn (slow - - 8.0 2.7
release particle)
~1~l (fast release 22.5 - - 22.5
particle)
r~.~L (slow rdease - 22.5 22.5
particle)
DETPMP - - 0.5 0.8
EDDS (fast release particle) 0.6 0.6
Protease 0.55
Protease (slow release - 0.60 0.55 1.27
particle)
Lipase 0.15 0.15 0.15 0.15
Cellulase G ~ 0.28 0.28 0.28
wogs/2s46s i~ 1 ~ 7~Q2 r ~ 6
63
Amylase 0.27 0.27 0.27 0.27
r~lywlJu~' 5.1 5.1 5.1 5.1
CMC 0.4 0.4 0.4 0.4
PVNO 0.03 0.03 0.03 0.03
Granular suds suppressor 1.5 1.5 1.5 1.5
Minu~ ;s~, to 100%
The following TgO values (in seconds) were obtained for each of products A to D
T80 A B C D
protease < 60 > 90 > 90 > 90
heavy metal ion sequestrant < 60 < 60 < 60 < oO
(DETPMP or EDDS)
W0 95/28468 ~) ~ 8 7 3 ~ 2 P~ 6
C~ ~Iti.~ testin~
Test - ' - stain ~emoval
S ~"r.yA, .. ~
Three white cotton sheets were prewashed in a non-biological bleach-free heavy duty
detergent. Sets of siA- test swatches of size 6cm x 6cm were cut from each sheet.
Stains were evenly painted onto each swatch set.
Additionally, pre-prepared swatches obtained from the EMPA institute were also
employed.
In summary, the following sets of swatches were employed:
~S '' s~ -
~MPA Blood;
Wine;
G~P~CV
Make-up;
r
Clay;
The sets of fabric swatches were subjected to one wash cycle in an automatic washing
machine The swatches were then assessed for removal of the stains by an expert
panel using a four point Scheffe scale. The combined averaged paired results of each
of the sets of, . are as set out below, with prior art I I A being
used as the common reference.
wo95/28468 6s P~ 6
In more detail, a Miele 698 WM automatic washing machine was employed, and the
40C short cycle ~ "~ selected. Water of 12 German hardness ( Ca: Mg = 3
: 1) was used. 75g of detergent, dispensed from a granulette dispensing device placed
in the middle of the load was employed. One swatch of each type ~vas washed along
with a ballast load of 2.7 Kg of lightly soiled sheets (1 weeks domestic usage).
ComDarative testin~ - stain removal
The above stain removal test method was followed in comparing the efficiency of
C~ . B, having a difference of 60 seconds for the T80 values of the protease
and ~DDS, with the reference prior art Co l~ A in removing different type of
stains.
The results obtained were as follows:
Stain tyDe stairl removal beneflt (PSU)
EMPA blood + 1.6
Wine + 1.4
Make-up + 1.1
Clay + 1.2
~s~..;r.~,l at 95% confidence limit
W095128468 ~ 3~ I~ 6
66
Example 2
The following bleach-containing machine ~ .u.. ,~ ;.. ,. were prepared
(parts by weight) in accord with the invention.
A B C D E F G
Citrate 15.0 15.0 15.0 15.0 15.0 15.0
480N6.0 6.0 6.0 6.0 6.0 6.0
Carbonate 17.5 17.5 17.5 17.5 17.5 17.5
Phosphate - - - - - - 38.0
Silicate (as 8.0 8.0 8.0 8.0 8.0 8.0 14.0
sio,)
'1 .2 1.2 1.2 1.2 1.2 1.2 2.5
(as SiO2)
PBl1.2 1.2 1.5 1.5 1.5 2.2 1.2
TAED (slow 2.2 2.2 2.2 3.5 - 2.2 2.2
release partide)
Cationic lactam - - - - 3.3
Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5
sismuth - 0.2 0.2 0.2 0.3 0.4 0.2
nitrate
Pwtease 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Amylase 1.5 1.5 1.5 1.5 1.5 1.5
Woss/2s468 ~ l 8 7 ~ 0 ~ . ~,l/U_,~ 6
BSA~ - 1.5
DETPMP 0.13 0.13 0.13 0.13 0.13 0.13
HEDP 1.0 1.0 1.0 1.0 1.0 1.0
Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5
Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3
misc inc
moisture to
balance
pH (1% 10.7 10.7 10.7 10.7 10.7 10.7 11.0
solution)
