DETERGENT COMPOSITIONS INHIBITING DYE TRANSFER CONTAINING A CATALYST, AMINE STABILIZER AND PEROXIDE GENERATING ENZYME

COMPOSITIONS DETERGENTES INHIBANT LE TRANSFERT DE COLORANTS RENFERMANT UN CATALYSEUR, UN AGENT STABILISANT AMINE ET UNE ENZYME PRODUISANT DU PEROXYDE

English Abstract

Dye transfer inhibiting compositions are disclosed, comprising: A) a metallo catalyst selected from a) metallo porphin and
water-soluble or water-dispersable derivatives thereof; b) metallo porphyrin and water-soluble or water-dispersable derivatives
thereof; c) metallo phthalocyanine and water-soluble or water-dispersable derivatives thereof; B) an amine base catalyst
stabilizer capable of binding to the 5th ligand of the metallo catalyst; C) an enzymatic system capable of generating hydrogen peroxide.

French Abstract

On divulgue des compositions pour inhiber le transfert de colorant comprenant : A) un métallocatalyseur choisi parmi a) une métalloporphine et un dérivé de cette dernière soluble et dispersible dans l'eau; b) une métalloporphyrine et un dérivé de cette dernière soluble et dispersible dans l'eau; c) une métallophtalocyanine et un dérivé de cette dernière soluble et dispersible dans l'eau; B) un stabilisateur de catalyseur à base d'amine capable de se fixer au cinquième ligand du métallocatalyseur; C) un système enzymatique capable de générer du peroxyde d'hydrogène.

Claims

CLAIMS:
1. A dye transfer inhibiting composition
comprising:
A. A metallo bleach catalyst selected from
a) metallo porphin and water-soluble or water-dispersable
derivatives thereof,
b) metallo porphyrin and water-soluble or
water-dispersable derivatives thereof,
c) metallo phthalocyanine and water-soluble or
water-dispersable derivatives thereof; wherein said metallo bleach
catalyst is present in an amount sufficient to provide a wash
solution at a concentration of from 10-8 to 10-3 molar;
B. an amine base catalyst stabilizer capable of binding
the 5th ligand of the metallo bleach catalyst and capable of
reducing the rate of self-destruction of said metallo bleach
catalyst; said catalyst stabilizer is selected from the group
consisting of imidazole compounds, pyridine compounds,
alkylated pyridine compounds, pyrole compounds,
(C2H5)3N,C3H7NH2,(C6H11)2NH,1,5-diazabicyclo(4,3,0)non-5-ene and
mixtures thereof, and is present in said composition in a
molar ratio of metallo bleach catalyst to catalyst stabilizer
of from 1:1 to 1:5,000; and
C. an enzymatic system capable of generating hydrogen
peroxide present in an amount capable of yielding hydrogen
peroxide at a concentration of from 0.005 to 10 ppm/min in
said wash solution.
2. A dye transfer inhibiting compositions according
to claim 1 wherein said amine base catalyst stabilizer is
selected from imidazole and derivates thereof.
3. A dye transfer inhibiting composition according
to claim 1 wherein said amine base catalyst stabilizer is
selected from pyridine and its derivatives thereof.

21
4. A dye transfer inhibiting composition according
to claim 1-3 wherein said enzymatic system comprises an
oxidase and as a substrate an alcohol, an aldehyde or a
combination of both.
5. A dye transfer inhibiting composition according
to any one of claims 1-3, containing a metallo porphin
derivative, wherein said iron porphin is substituted on at
least one of its meso positions with a phenyl or pyridyl
substituent selected from the group consisting of
<IMG> and <IMG>
wherein n and m may be 0 or 1, A is selected from the group
consisting of sulfate, sulfonate, phosphate, and carboxylate
groups, and B is selected from the group consisting of C1-C10
alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.
6. A dye transfer inhibiting composition according
to claim 5 wherein the substituents on the phenyl or pyridyl
groups are selected from the group consisting of -CH3, -C2H5,
-CH2CH2CH2SO3-, -CH2COO-, -CH2C-H(OH)CH2SO3-, and -SO3.
7. A dye transfer inhibiting composition according
to any one of claims 1-3, containing a metallo porphin
derivative, wherein said metallo porphin is substituted on at
least one of its meso positions with a phenyl substituent
selected from the group consisting of
<IMG>

22
wherein X1 is (=CY-) wherein each Y, independently, is
hydrogen, chlorine, bromine or meso substituted alkyl,
cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.
8. A dye transfer inhibiting composition according
to claim 7 wherein the catalyst compound is metallo
tetrasulfonated tetraphenylporphin.
9. A dye transfer inhibiting composition according
to claim 1 wherein the metallo of said metallo catalyst is
substituted by Fe, Mn, Co, or other transition metals.
10. A dye transfer inhibiting composition according
to claim 1 wherein the concentration of metallo catalyst is
from 10-8 to 10-3 molar, preferably from 10-6 to 10-4 molar.
11. A dye transfer inhibiting composition according
to claim 4 wherein the oxidase is present by 0.1 - 20000
units, preferably 0.5 to 5000 units per gram of the
composition.
12. A dye transfer inhibiting composition according
to claim 4 wherein said substrate is glucose.
13. A dye transfer inhibiting composition according
to claim 4 wherein said substrate consists of a C1-C6 alcohol.
14. A dye transfer inhibiting composition according
to claim 10 wherein said substrate is ethanol.
15. A dye transfer inhibiting composition according
to claim 3 in which the substrate is present from 0.1 to 50%
by weight of the composition.
16. A dye transfer inhibiting composition according
to claim 1 which yields hydrogen peroxide at a concentration
from 0.005 to 10 ppm/min in the wash process.

23
17. A dye transfer inhibiting composition according
to claim 1 wherein said catalyst stabilizer is present in a
molar ratio of iron porphin to amine base catalyst from 1:1
to 1:5000, preferably from 1:1 to 1:2500.
18. A dye transfer inhibiting composition according
to any one of claims 1-3, 5-6 or 8-17 which is a detergent
additive, in the form of a non-dusting granule or a liquid.
19. A detergent composition which comprises a dye
transfer inhibiting composition according to any one of
claims 1-3, 5-6 or 8-17 of the preceding claims further
comprising enzymes, surfactants, builders, and other
conventional detergent ingredients.
20. A process for inhibiting dye transfer between
fabrics during laundering operations involving colored
fabrics, said process comprising contacting said fabrics with
a laundering solution containing a dye transfer inhibition
composition according to any one of claims 1-3, 5-6 or 8-17.
21. A process for inhibiting dye transfer according
to claim 20 which is carried out at a temperature in the
range of from 5°C to 90°C.
22. A process for inhibiting dye transfer according
to claim 20 wherein the pH of the bleaching bath is from 7 to
11.
23. A process for inhibiting dye transfer according
to claim 22 wherein the pH of the bleaching bath is from 7 to
9.
24. A process for inhibiting dye transfer according
to claim 21 wherein the pH of the bleaching bath is from 7 to
11.

24
25. A dye transfer inhibiting composition according
to claim 4 which is a detergent additive, in the form of a
non-dusting granule or a liquid.
26. A dye transfer inhibiting composition according
to claim 7 which is a detergent additive, in the form of a
non-dusting granule or a liquid.
27. A detergent composition which comprises a dye
transfer inhibiting composition according to claim 4 further
comprising enzymes, surfactants, builders, and other
conventional detergent ingredients.
28. A detergent composition which comprises a dye
transfer inhibiting composition according to claim 7 further
comprising enzymes, surfactants, builders, and other
conventional detergent ingredients.
29. A process for inhibiting dye transfer between
fabrics during laundering operations involving colored
fabrics, said process comprising contacting said fabrics with
a laundering solution containing a dye transfer inhibition
composition according to claim 4.
30. A process for inhibiting dye transfer between
fabrics during laundering operations involving colored
fabrics, said process comprising contacting said fabrics with
a laundering solution containing a dye transfer inhibition
composition according to claim 7.
31. A dye transfer inhibiting composition according
to claim 4, containing a metallo porphin derivative, wherein
said iron porphin is substituted on at least one of its meso
positions with a phenyl or pyridyl substituent selected from
the group consisting of
<IM> and <IMG>
.

wherein n and m may be 0 or 1, A is selected from the group
consisting of sulfate, sulfonate, phosphate, and carboxylate
groups, and B is selected from the group consisting of C1-C10
alkyl, C1-C10 polyethoxyalkyl and C1-C10 hydroxyalkyl.
32. A dye transfer inhibiting composition according
to claim 4, containing a metallo porphin derivative, wherein
said metallo porphin is substituted on at least one of its
meso positions with a phenyl substituent selected from the
group consisting of
<IMG>
wherein X1 is (=CY-) wherein each Y, independently, is
hydrogen, chlorine, bromine or meso substituted alkyl,
cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl.

Description

~i~93~15176 PCT/US93/~626
2127096
~clt~GtNT COMPOSITIONS INHIBITIN6 DYE TRANSFER CONTAININ6
A CATALYST, AMINE STABILIZER AND PF~O~I~F 6ENERATIN6 ENZYME
.
.
F;~ld~of the Tnvention
.
Ti~e ~ ent il-~e~.Lion relates to a composition and a process -~
for ir~hibiting dye transfer between fabrics during wa~ki~
: ~ ,
,~ ' .
Bac~Loul-d of the Invention
One of the most persistent and troublesome problems arising
during modern fabric laundering operations is the ten~ency of
~ome colored fabrics to release dye into the laundering
solutions. The dye is then transferred on~o other fabrics
being washed therewith.
one way of overcoming this problem would be to bleach the
fugitive dyes'washed out of dyed fabrics before they have the
opportunity to become at~ch~ to other articles in the wash.
S~ r-nA~d or solubilized dyes can to some degree be ~ i 7
~; in solution by employing known bleaching agents.

og3/15176 ~ 12~ 09 6 PCT/US93/~626-
~
GB 2 101 167 describes a stable liquid bleaching compositioncontaining a hydrogen peroxide precursor which is activated to
yield hydrogen peroxide on dil:tion.
However it is important at ~hè same time not to bleach the
dyes actually remaining on thè fabrics, that is, not to cause
color damage.
U.S. Patent 4,077,768 describes a process for inhibiting dye
transfer by the use of an oxidizing bleaching agent together
with a catalytic compound such as iron porphinc.
Cop~ndi~g EP Patent Application 91202655.6 filed October 9,
991, relates to dye transfer i~hihiting compositions ~-
comprising an enzymatic system c~p~hle of generating hydrogen
peroYi~ and ~GL~hin catalysts.
It has now been found that certain amine base catalys
stabilizers when added to said enzymatic dye transfer
i ~ i h~ting compositions enhances the overall performance of
said compositions.~
The addition of said catalyst stabilizers re~ the rate of
s-If-de_L ction of the porphin catalyst ~ ting in im~rovel
through-th~ St ~h, stability of the porphin catalyst.
Also, imp.~ved whiteness benefits are obt~inP~ in the presence
of catalyst stabilizers, due to a substantial reduction in the
amount of porphin catalyst deposited onto the fabrics.
Furthermore, it has been found that said catalyst stabilizers -~
accelerate the oxidation reactivity of the ~oL~hin catalyst
thereby încreasing the rate of the dye bleaching. ' ''
Accor~in11y, a dye transfer i nh ~ hiting composition is
provided which exhibits optimum dye transfer inhibiting
properties.
~ , -
R~ot~ing to another embodiment, the invention provides an
efficient p~o~e for laundering operations involving colored
fabrics.
: . .

'~ ~ g3/lsl76 2 1 2 7 0 9 6 PCT/USg3/~K26
Summarv of the Invention
The present invention relates to inhibiting dye transfer
compositions comprising :
A. a metallo catalyst selected from
a) metallo porphin and water-soluble or water-
~i~r~rsable derivatives thereof;
b) metallo ~oL~hy~in and water-soluble or
water-Ai~r~rsable derivatives thereof;
c) metallo phthalocyanine and water-soluble or
water-~isrersable derivativas thereof;
~, 8~. an amine base catalyst stabilizer capable of bin~in~ to
the 5th ligand of the metallo catàlyst.
C. an enzymatic system c~pAhle of generating hyd~o~en
peroxide. '
~ -c~ing to another embodiment of this invention a ~c ~r-
is also provided for laundering operations involving colored
fabrics. ~;
Detail~ de~cription of the invention
The present invention provides a dye transfer inhibiting
composition comprising :
A. a metallo catalyst selected from
a) metallo porphin and water-soluble or watex~
Ai ~r rsable derivatives thereof;
b) metallo porphyrin and water-soluble or
water-~isr~rsable derivatives thereof;
c) metallo phthalocyanine and water-soluble or
water-dispersable derivatives thereof;
.
B. an amin- base catalyst stabilizer rAp~hle of binAin~ to
the Sth ligand of the metallo catalyst.
C. an enzymatic system cAp~hle of qenerating hydrogen
peroxide.

wo 93/lsli6 o 9 6 pcr/us93~oo62~r
The Hvdroqen Peroxide Precursor
The oxidizing agent, hydrogen peroxide is generated in situ
by usinq an enzymatic hydrogen peroxide generation system.
The use of an enzymatic hydrogen peroxide generating system
allows the continuous generation of low levels of hyd~Gyen
peroxide and provides a practical way of controlling a low
steady-state level of hyd~o~en peroxide. Maximum effectiveness
occurs when the component levels are such that the hydrogen
peroxide is repl~ni~ at a rate similar to its removal due to
the oxidation of dyes in the wash water. ~;
The enzyme used~in the ~ ent invention is an ox~ e.
The oxidase is y~-?nt by 0.1 - 20000 units, preferably 0.5 to
5000 units per gram of the composition. One unit is the amount
of enzyme needed to convert 1 mol of substrate per minute.
Suitable QYi ~ are urate oxidase, galactose oxidase,
alcohol QXi ~ 5 ~ amine oYi~es, amino acid oxi~A~e.c,
cholesterol oY~ e and glucose oxidase, malate oxidase,
glycollate QYi A-~? ~ hexose oxidase, aryl alcohol oxidase, L~
gulonolactose oxi~a~o~ pyranose oxidase,
L ~or~o~e ~x~ e, pyri~oYine 4-oxidase, 2-2 hydlo~acid c
oYi~rq, choline nxi~a~e, ecdysone oxi~e.
The preferred enzymatic systems are alcohol and aldehyde
QYi ~ses, gl~cQc~ oxidase.
The more preferred systems for granular detergent application
would have solid alcohols, e.g. glucose whose oxidation is
catalysed by glu-:-? oxidase to glucoronic acid with the
formation of hydLG~ peroxide.
The more preferred systems for liquid detergent application
would involve liquid alcohols which could for example, also act
as solvents. An example is ethanol/ethanol oxidase.
The quantity of oxidase to be employed in compositions
according to the ill~e--~ion should be at least sufficient to
provide in the wash a constant generation of 0.005 to 10 ppm
AvO per minute. For example, with the glucose oxidase , this
can be achieved at room temperature and at pH 6 to 11,
preferentially 7 to 9 with 1-20000 U/l gl~co~e oxidase, 0.00s

wo g3/lsl76 2 1 2 7 0 9 6 PCT/USg~/ ~ 26
s
to o.s % giucose under constant aeration in the washing
process.
Metallo catalvst
The preferred usage range of the .catalyst in the wash is 10-8
molar to 10-3 molar, more preferred 10-6 - 10-4 molar.
The e~?ntial metallo porphin structure may be visualized as
indicated in Formula I in the accompanying drawings. In
Formula I the atom positions of the porphin structure are
numbered conventionally and the double bonds are put in
conventionally. In other formula, the double bonds have been ~ :
omitted in the dr~wings, but are actu~lly ~ nt a8 in I.
'
Prefersed metallo porphin stru~u~e_ are ~o~e substituted at
one or more of the 5, 10, 15 and 20 carbon positions of Formula
I (Meso posîtions), with a ~he..~l or pyridyl substituent
.selected from the group consisting of .
_0)~-O~
wh-rein n and m may be O or l; A may be sulfate, sulfonate,
phosphate or c~rh~ylate groups; and B is Cl-C10 alkyl,
polyethoxy alkyl or hydroxy alkyl.
Preferred molecules are those in which the substituents on -
the phenyl or pyridyl ~LGu~s are selected from the ~ou~ :
consisting of
-CH3, -C2Hs, -CH2CH2CH2S03-, -CH2--, and -CH2CH(OH)CH2S03-, -
so3
A particularly preferred metallo phorphin is one in which the
molecule is substituted at the 5, 10 15, and 20 carbon ':
positions with the substituent
~\S03~ '
":

W093/15176 PCT/US93/~626
2~2~ o 9 6 6
- This preferred compound is known as metallo tetrasulfonated
tetraphenylporphin. The symbol xl is (=cY-) wherein each Y,
independently, is hydrogen, chlorine, bromine or meso
substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or
heteroaryl. .
The symbol x2 of Formula I represents an anion, preferably
OH- or Cl-. The com~oul.d of Formula I may be substituted at
one or more of the remaining carbon positions with Cl-ClO
alkyl, hy~loxyalkyl or oxyalkyl ~lOU~
l7
lS~ / S
13 ~ (I)
Porphin derivatives also include chlorophyls, chlorines, i.e. '~-~
isobacterio chlorines and bacteriochlorines.
Metallo ~o.~hylin and water-soluble or water-dispersable
derivatives thereof have a structure given in formula II.
X~X
~2 ~ ~
x
X ~ (II)
where X can be alkyl, alkyl carboxy, alkyl hydroxyl, vinyl,
alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate,
aryl.
The symbol x2 of Formula II represents an anion, preferably
OH- or Cl-.
The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl,
vinyl, Alkenyl, alkylsulfate, alkylsulfonate, sulfate,
sulfonate.

WO g3/15176 2 1 2 7 0 9 6 PCT/US93/~K26
Metallo phthalocyanine and derivatives have the structure
indicated in Formula III, wherein the atom positions of the
phthalocyanine structure are numbered conventionally. The
anionic groups in the above structures contain cations selected
from the ~LoU~ consisting of sodium and potassium cations or
other non-interfering cations which leave the structures water-
soluble. Preferred phthalocyAni r.e derivatives are metallo
phthalocyAnine trisulfonate and metallo phthalocyanine
tetrasulfonate.
p~5
~15 ~ (III)
Another form of substitution possible for the present
h.~e..~ion is sukstitution of the central metal by Fe, Mn, Co
Rh, Cr, Ru, Mo or other transition metals.
Still a number of considerations are significant in selecting
variants of or substituents in the basic porphin or azaporphin
structure. In the first place, one would choo~e com~ou,.ds
which are available or can be readily synthesized.
'
~ y~..d this, the choice of the substituent groups can be used
to control the solubility of the catalyst in water or in
detergent solutions. Yet again, especially where it is desired
to avoid attacking dyes attached to solid surfaces, the
substituents can control the affinity of the catalyst compound
for the surface. Thus, strongly negatively charged substituted
compounds, for instance the tetrasulfonated porphin, may be -
repelled by nçgatively charged stains or stained surfaces and
are therefore most likely not to cause attack on fixed dyes,
whereas the cationic or zwitterionic compounds may be -

WO g3/15176 PCr/US93/00626
2l2 7og6
attracted to, or at least not repelled by such stained
surfaces.
Amine base catalYst stabilizer
The dye transfer inhibiting benefits can be optimized by adding
small amounts of catalyst stabilizers.
It is well known in art that catalyst e.g. metallo porphins are ~;
~ certible to self-destruction. As a result of said
selfdestruction, the level of catalyst sh4~lld be such that
sufficient active catalyst is present to bleach the dyes ~~ ~
throughout the total wash cycle. ~'
It has now been found that the stability of metallo catalyst
used in the pL~ -ent invention is i~ ved by A~Ain~ amine base
catalyst stabilizers carAhle of bin~in~ the 5th ligand of the
central atom in the metallo porphin structure. Preferred
hete~G~lic compounds suitable for the present invention are
imidazole compounds of the formula :
RiC - CH-X-R2 -.
N N-Y
Rl
wherein Y is hydrogen or oxygen or a Cl-C12 alkyl,
Ri, Rl and R2 are selected inA~penAently hydrogen or Cl-C30
alkyl or alkenyl ~LOu~_~ and X is selected from the group of :
R3 N C
~ I ~I ,.
R4 ~
R3 ~ C
O
, .:

- WO g3/15176 2 1 2 7 0 9 6 PCT/US931~K26
~3
R3 ~ ~
wherein R3 is a Cl-C5 alkanediyl group, or is ~ ;
(CH CH2 ~)n (CH2 CH2)~
"' ~ '- . '
'
- R4
~with n~being an integer from O to 10, and m is an integer from -.
O~to 2~ n+m>1, and R4 being a Cl_4 alkyl group or hy~ en. ;
Xost~preferred are im~ ole derivatives incl~in~ histidine,
purines,~ hiroYanthine, i-idazolidica-Lo~lic acid, histamine,
polyhistidine~, alkylated imidazole.
Other hete-o~lic compounds suitable for the p-~-ent
invention are pyridine and alkylated pyri~in~~ and derivatives
thereof, pyrole and derivatives thereof.
~ Non hete~o~y~lic com~o~ s capable of binAing the 5th ligand
of the central atom in the porphin structure are suitable for
the present invention.
These non heterocyclic comro~n~C include non heteLG~olic
amines, having the formula (C2Hs)3N, C3H7NH2, (C6Hll)2NH, 1,5 -
diazabicyclot4.3.0]non-5-ene.
'
~eoon~, the catalyst stabilizers of the present invention
r~ e the deposition of the porphin catalyst onto the fabric,
resulting ' better whi~enQr~ main~nAnc~ of white fabrics.
Also, it has been found that the addition of the catalyst
stabilizers mentioned hereinabove not only ~ ts in less '~
self-deJtruction of the structure but also L~-ults in less ---~
~d-position of oxi~i7ed or non oxidized ~o~hin. ~ '-
': '

WOg3/15176 PCT/US93/~626~
2~ og6 10
~ Furthermore, it has been found that the rate of dye oxidation
by the porphin catalyst is greatly enhanced by the presence of
the said catalyst stabilizers. This results in an increased
dye bleaching.
The amine base catalyst stabili~er is present in a molar ratio
of iron porphin to amine base catalyst from 1:1 to 1:5000,
preferably from 1:1 to 1:2500.
The p~.-ent compositions are conveniently used as additives
to conventional detergent compositions for use in laundry
operations.
The present invention also encompA~er dye transfer inhibiting
compositions which will contain detergent i..~Lelients and thus
serve as detergent compositions.
~ . .
;K~;r. ~ ING~ TF~JTS
A wide range of surfactants can be used in the detergent
compositions. A typical listinq of anionic, nonionic,
ampholytic and zwitterionic cl~c~~c, and species of these
surfactants, is given in US Patent 3,664,961 i~ to
Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable
herein, especially mixtures of sulphonate and sulphate
surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred
sulphonates include alkyl benzene sulphonates having from 9
to 15, e~p~cially 11 to 13 carbon atoms in the alkyl
radical, and alpha-sulphonated methyl fatty acid esters in
which the fatty acid is derived from a C12-C18 fatty source
preferably from a C16-Clg fatty source. In each instance
the cation is an alkali metal, preferably sodium. Preferred
sulphate surfactants are alkyl sulphates having from 12 to
18 carbon atoms in the alkyl radical, optionally in
admixture with ethoxy sulphates having from 10 to 20,
preferably 10 to 16 carbon atoms in the alkyl radical and an
average degree of ethoxylation of 1 to 6. Examples of -
preferred alkyl sulphates herein are tallow alkyl sulphate, ~

WO93/15176 2 1 2 7 0 9 6 PCT/US93/~626
coconut alkyl sulphate, and cl4_15 alkyl sulphates. The
cation in each instance is again an alkali metal cation,
preferably sodium.
One class of nonionic surfactants useful in the present
invention are condensates of ethylene oxide with a
hydrophobic moiety to provide a surfactant having an average
hydrophilic-lirorhilic h~l~nce (HLB) in the range from 8 to
17, preferably from 9.5 to 13.5, more preferably from 10 to
12.5. The hydrophobic (lipophilic) moiety may be aliphatic
or aromatic in nature and the length of the polyoxyethylene
~c~p which is condensed with any particular hydrophobic
group can be readily adjusted to yield a water-soluble
compound having the desired d~.ee of balance between
hydrophilic and hy~o~ ~ic elements.
'~cr~cially preferred nonionic surfactants of this type are
the Cg-Cls primary alcohol ethoxylates cont~ining 3-8 moles
of ethylene oxide per mole of alcohol, particularly the C14-
C15 primary alcohols contAining 6-8 moles of ethylene oxide
per mole of alcohol and the C12-C14 primary alcohols
con~inin~ 3-5 moles of ethylene oxide per mole of alcohol.
Another cl A~C of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO (CnH2nO)tzx
wherein Z is a moiety derived from glucose, R is a saturated
hydrophobic alkyl group that contains fr~m 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to
4, the com~o~ C including less than 10% unreacted fatty
alcohol and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent are
disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
Also suitable as nonionic surfactants are polyhydroxy
fatty acid amide surfactants of the formula
R2 _ C - N - Z,
~: '
O Rl '

WO93/15176 PCT/US93/~626
2127 Og6 12
wherein Rl is H, or R1 is Cl_4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is C5_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
- linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, Rl is methyl, R2 is a straight Cll_l5
alkyl or alkenyl chain such as coconut alkyl or mixtures
thereof, and Z is derived from a reducing sugar such as
gl~o~e, fructose, maltose, lactose, in a reductive
amination reaction.
The compositions accordinq to the p~~ent invention may
further comprise a builder system. Any conventional builder
system is suitable for use herein including aluminosilicate
materials, silicates, polycarboxylates and fatty acids,
materials such as ethyle,~ amine tetraacetate, metal ion
sequestrants such as aminopolyphocrhonates, particularly
ethylenediamine tetramethylene phosphonic acid and diethylene
triamine pentamethyleneph~ OI~ic acid. Tho~h less preferred
for obvious environmental reasons, phQ~r~te builders can also
be used herein.
Suitable builders can be an inorganic ion exchange material,
commonly an inorganic hydrated aluminosilicate material, more
particularly a hydrated synthetic zeolite such as hydrated
zeolite A, X, B or HS.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered
silicate consisting of sodium silicate (Na2Si205).
Suitable polycarboxylates builders for use herein include
citric acid, preferably in the form of a water-soluble salt,
derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH)
wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or
wherein R can be substituted with hydroxyl, sulfo sulfoxyl or
sulfone substituents. Specific examples include lauryl
succinate , myristyl succinate, palmityl succinate2-
~o~ecenylsuccinate, 2-tetradecenyl succinate. Succinate - -
builders are preferably used in the form of their water-soluble ~
~ .

WO93/15176 2 1 2 7 0 9 ~ PCT/US93/~K26
salts, including sodium, potassium, ammonium and alkanolammonium
salts.
Other suitable polycarboxylates are oxodisuccinates and
mixtures of tartrate monosuccinic and tartrate disuccinic acid
such as described in US 4,663,071.
Especially for the liquid execution herein, suitable fatty
acid builders for use herein are saturated or unsaturated C10-18
fatty acids, as well as the COL~_POnA; ng soaps. Preferred
saturated species have from 12 to 16 carbon atoms in the alkyl
chain. The preferred unsaturated fatty acid is oleic acid.
Another preferred builder system for liquid compositions is
- h~ on ~o~cçnyl s~ccinic acid.
- Preferred builder systems for use in granular compositions
include a mix~e of a water-insoluble aluminosilicate builder
such as zeolite A, and a watersoluble carboxylate chelating
agent such as citric acid.
Other buildèr materials that can form part of the builder -~
system for use in grannl~r compositions for the pu~ ee of this
invention include inorganic materials such as ~ i metal
carbonates, birarbo~-tes, silicates, and organic materials such ~-~
as the organic ph-sr~onates, amino polyalkylene phosphonates and
amino polyca~Loxylates.
Other suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the polyca~o~ylic
acid comprises at least two carboxyl radicals separated from
each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers having a
molecular weight of from 20,000 to 70,000, especially about
40,000.
Detergency builder salts are normally included in
amounts of from 10% to 80% by weight of the composition
preferably from 20% to 70% and most ~ lly from 30% to
60% by weight.
The compositions of the pL~ -ent i--v~ ion ~ho~ld be
free from ~G.Ivention~l bleaching agents. Other components
used in detergent compositions may be employed, such as
suds ~OG_ Ling or depressing agents, enzymes and
.
:

WO93/15176 PCT/US93/~626~
2~ o96 14
stabilizers or activators therefore, soil-suspending
aqents soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring
agents, and perfumes. Especially preferred are
combinations with enzyme technologies which also provide
a type of color care benefit. Examples are cellulase for
color maintenance/ rejuvenation.
These components, particularly the enzymes, optical
brighteners, coloring agents, and perfumes, should
preferably be cho~~n such that they are compatible with
the bleach component of the composition.
The detergent compositions according to the invention
can be in liquid, paste or granular forms. Granular
compositions according to the present invention can also
be in "compact form", i.e. they may have a relatively
higher density than cG..ventional granular detergents,
i.e. from 550 to 950 g/l; in such case, the granular
detergent compositions according to the present invention
will contain a lower amount of "inorganic filler salt",
compared to conventional granula~r detergents; typical
filler salts are A~ ine earth metal salts of sulphates
and chlorides, typically sodium sulphate; "compact"
detergents typically comprise not more than 10% filler
salt.
The present invention also ralates to a process for
inhibiting dye transfer from one fabric to another of
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
The process comprises contacting fabrics with a laundering
solution as hereinbefore described.
The process of the invention is conveniently carried out in
the course of the washing process. The washing process is
preferably carried out at 5-C to 90-C, especially 20 to 60, but
the catalysts are effective at up to 95-C. The pH of the
treatment solution is preferably from 7 to 11, especially from ~"
7.0 to g.o. ~

~og3/lsl76 2 1 2 7 0 9 ~ PCT/US93/~K26
The process and compositions of the invention can also be
used as additive during laundry operations.
The following examples are meant to exemplify compositions of
the present invention, but are not n~cecQ~rily meant to limit
or otherwise define the scope of the invention, said scope
being determined according to claims which follow.
EXUIID1~ 1
~omc~c~-~us ~ye bloaching
The extent of dye oxidation was compared between a composition
containing imidazole as amine base catalyst and a system without
amine base catalyst. -~
~ '~
Composition A: A detergent solution tlOOmL) cont~inin~ dyes (40
ppm final ~c~centration), gl~o-e (0.}% by weight) and a ferric
tetrasulfonated tetrAp~nylporphin catalyst (l x lO-5 M) was
~erAred and its pH value adjusted to 8Ø
Composition B: A detergent solution (lOOmL) containin~ dyes (40 ~
ppm final concentrat.ion), gl~Q~? (0.1% by weight), and ferric -~;
tetrasulfonated tetraphenylporphin catalyst (2.5 x 10-6 M) and
imidazole (lO mM) was prepared and its pH value adjusted to pH
8Ø
Test method :
The absorbance spectrum was recorded (350-750 nm). This region
encomr~e~ the wavelength maximum of the dyes (as noted in the
table below) and the Soret band of the catalyst (414 nm).
Glucose oxidase (final concentration O.lU/mL) was then added to
the stirred solution to initiate the reaction. After 30 min the
absorbance a~e_~rum was recorded and the decrease in the
absorbance maximum of the dyes noted.
Blank experiments indicated that n~ oxidation of the dyes
occurred over the same period in the absence of catalyst or ''
gl~rQ~ oxidase.

W093/15176 PCT/US93/~626 -
9 6 16
.
, % destruction of dye
Dy~s CI # l~x COMP A COMP B
Acid Blue 9 42000 630 nm 13 53
Direct blue 98 23155 570 nm 62 90
Direct blue 120 34090 570 nm 50 83
Acid blue 113 26360 595 nm 39 95
FD&C Red 40 16035 500 nm 0 30
Acid Yellow 40 18950 440 nm 0 30
Conclusion : Even though a lower level of iron porphin catalyst
iS ~L -?nt in composition B, dyes are ,oxidized to a much bigger
extent compared to composition A containing 4 times the iron
porphin catalyst level.
~m~l~ 2
8t~b~lity of the ~etallo catalysts
The -tabllity of different po~yh~Lins and phthalocya~ine~ was ;~"'~
dete~rmined in the ~L~ Ce of imidazole as amine base catalyst. ;'~
A,d'etergent solution (lOOmL) of glucose (0.1% by weight) and
di~ferent metallo catalysts (10 x 10-5 M) was prepared and the
pH adjusted to 8Ø To initiate ~he reaction, different levels
of glucose oxidase were~ . The destruction of the catalyst
was measured in each case by quantifying the decrease in
absorption of the Soret band (414 nm). '-'
The catalyst destruction was compared with and without imidazole
at different time intervals.

93/15176 2I27096 PCr/US93/00626
17
% calalyst destrucUon
U Glox/ mL No ~With 10 mM imid~zole
10 min 20 min 30 min 10 min 20 min 30 min
Iron Tetra~ultonat~d ~etr~phenylporphin
0.1 53 7 0 92 87 82
H~min chl~lde
0.05 67 42 29 100 93
0.25 33 21 13 92 68 49 ~ '
Iron ph~ nin~ unon~t~d
0.05 69 31 18 88 85 ~2 ~
o.l 47 16 0 88 83 80 : -
nophth~locy~nin-t~ulhn-t~d -
O1 30 0 ~ 77
EX~D1e 3
D-position of F~.r~
'
A 50 mM borate buffer solution tPH 8.0) of ferric
tetrasulfonated tetraphenylporphin catalyst (FeTPPS) (10-5 M, 10
ppm by weight) was prepared. The FeTPPS ~rocition was studied
as follows: a knitted cotton fabric (~14g) wa8 6~k~ in the
FeTPPS solution (100 mL) for 15 min. At the end the fabric wa8
removed and the water squeezed out of it. A solution sample (2
mL) was ~en before and after soaking. The ~oncentration of
FeTPPS in the solution was determined spectrophotometrically
from the 2 ml sample by observing the absorbance peak at 414 nm
(characteristic of the FeTPPS Soret band).
This experimental procedure was repeated with and without
imidazole (10 mM).
solution % Porphyrin left in solution
FeTPPS only 50
FeTPPS+Imidazole 8~
Conclusion : The pr~-ence of imidazole strongly
re~-lc~s the ~on~oncy of FeTPPS to deposit onto
fabrics.

WO93/15176 PCT/US93/~62~
096 18
- Exam~le IV
A liquid dye transfer inhibiting composition according to the
present invention is prepared, having the following
compositions :
% .
Linear alkylbenzene sulfonate lO
Alkyl sulphate 4
Fatty alcohol (Cl2-Cl5) ethoxylate 12
Fatty acid l0
Oleic acid 4
Cit~ic acid l :~
NaOH 3.4
Propanediol l.5
Ethano} 5
Ethanoloxidase 5 u/ml
Ferric tetrasulfonated tetraphenylporphin O.l
imidazole 3
::
Minors up to lO0 ~-:
ExamDlè V
':.
A compact granular dye transfer inhibiting composition
a~G-ding to the present invention is prepared, having the
following formulation:
Linear alkyl benzene sulphonate ll.40
Tallow alkyl sulphate l.80
C45 alkyl sulphate 3.00
C45 alcohol 7 times ethoxylated 4.00
Tallow alcohol ll times ethoxylated l.80
Dispersant 0.07
Silicone fluid 0.80
Tri~oAium citrate 14.00
Citric acid 3.00
Zeolite 32.50
Maleic acid actylic acid copolymer 5.00
.

'~093/15176 2 I 2 7 0 9 6 PCT/US93/~626
19 ,:
DETMPA 1.00
Cellulase ~active protein) 0.03
~1kA lase/BAN 0.60
Lipase 0.36
Sodium silicate 2.00 :
Sodium sulphate 3.S0
Ferric tetrasulfonated tetraphenylporphin 0.025
Glucose 10.00
Glucose oxidase 100 u/ml
imidazole 3
Minors up to 100
, .
:: .