Note: Descriptions are shown in the official language in which they were submitted.
~: W094/1]477 2 1 ~ 8 8 1 1 PCT/US93tlO543
,3 1 .
DYE TRANSFER INHIBITING COMPOSITIONS CONTAINING A METALL~
CATALYST, A BLEACH & PO~YAMINE N-OXIDE POLYMER
**~*~***********
i
Field of the Invention
The present invention relates to a composition and a process
for inhibiting dye transfer between fabrics during washing.
Ba _ground of the Invention
,
Qne of the most persistent and troublesome problems arising
during modern fabric laundering operations is the tendency of
some colored fabrics` to release dye into the laundering
solutions. The dye is then transferred onto other fabrics
being washed therewith. ~-
One way of overcoming this problem would be to complex or
adsorb the fugitive dyes~washed out of dyed fabrics before
they h~ve the opportunity to become attached to other articles
in the wash.
:; : ' .-
:"
1`WO 94/11477 PCr/US93/10~43 :~
2 ~
Polymers have been used within detergent compositions to
inhibit dye transfer, such as disclosed in EP-A-102 923, DE-A-
2 814 329, FR-A-2 144 721 and EP-265 257.
Copending EP Patent Application 92202168.8 describes dye
transfer inhibiting compostions comprising polyamine N-oxides
containing polymers.
Another way of overcoming the problem of dye transfer would
be to bleach the fugitive dyes washed out of dyed fabrics
before they have the opportunity to become attached to other
articles in the wash.
Suspended or solubilized dyes can to some degree be oxidized
in solution by employing known bleaching agents.
GB 2 101 167 describes a stable liquid bleaching composition
containing a hydrogen peroxide precursor which is activated to
yield hydrogen peroxide on dilution.
However it is important at the same time not to bleach the
dyes actually remaining on the 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 porphins.
,
Copending EP Patent Application 91202655.6 filed October 9,
1991, relates to dye transfer inhibiting compositions
comprising an enzymatic system capable of generating hydro~en
peroxide and porphin catalysts.
It has now been surprisingly found that polyamine N-oxicle ~ `
polymers and metallo-catalysts provide superior and
synergistic dye transfer inhibiting propertles compared to the
catalyst- or polymers-system taken alone. This finding allows
to formulate compositions which exhibit excellent dye transfer
inhibiting properties with low level of catalysts, which in
turn, reduces the problem of catalyst deposition onto fabrics. .
According to anokher embodiment of this invention a process 1 1
is also provided for laundering operations involving colored - i fabrics.
i~
"
, 1.
, !WO 94/11477 PCT/US93/10543
:' ~ 3 2I~8811 j`~`
Summary of the Invention
'.
The present invention relates to inhibiting dye transfer
~ compositions comprising polyamine N-oxide containing polymers
~, and metallo catalysts and an efficlent amount of bleaching
1 agent.
''
.~ Detailed description of the invention
~j
~ Polyamine N-oxide contalning polymers
,,
;~ The compositions of the present invention comprise as an
1 essential element polyamine N oxide polymers which contain
. units having the following structure formula :
P
;~ Ax
i. R
l herein P is a polymerisable unit, whereto the R-N-O group
,, can be attached to or wherein ~.he R-N-O group
forms part of the polymerisable unit or a
combination of both.
' ' 11 R 1l ~ '
A is NC, CO, C, -O-,-S-, -N- ; x is or O or l;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any
combination thereof whereto the nitrogen of the N-
O group can be attached or wh~erein the nitrogen
of the N-O group is part of these groups.
~ W~ 94/1 1477 2 1 4 S ~ 1 ~ PCT/US93/10543 ~-
i , ~ .
The N-O group can be represented by the following general
~1 structures :
;~
O O '~
j(Rl)x -N- ~R2)y =N- (Rl~x
,~ I
(~3) z
wherein Rl, R2, R3 are ~liphatic groups, aromatic,
heterocyclic or alicyclic groups or combinations thereof,
x or/and y or/and z is 0 or l 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 polymerisable unit (P) or
can be attached to the polymeric backbone or a combination of
both.
Suitable polyamine N-oxides wherein the N-O group forms part
I of the pol~merisable unit comprise polyamine N-oxides wherein
j R is selected from aliphatic, aromatic, alicyclic or
~ heterocyclic groups.
I 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 heterocyclic group such as pyrridine, pyrrole,
imidazole, pyrrolidine, piperidine and derivatives thereof.
.
Another class of said polyamine N-oxldes comprises the group ,.
of polyamine N-oxides wherein the nitrogen of the N-O group is
attached to the R-group.~ I
Other suitable polyamine N-oxides are the polyamine oxides 1-
whereto the N-O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine
N-oxides having the general formula tI) wherein R is an
aromatic, heterocycllc or alicyclic groups wherein the
nitrogen of the N-0 functional group is part of said R group.
l .
W094~11477 21~ PCT/US93/1~43
: 1.
! Examples of these classes are polyamine oxides wherein R
is a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
.~
Another preferred class o~ polyamine N-oxides are the
polyamine oxides having the general formula (I) wherein R are
aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N-O 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, polyimides, polyacrylates and mixtures
thereof.
The amine N-oxide polymers of the present invention
typically have a ratio of amine to the amine N-oxide of lO : 1
to l: lQOOOOO. However the amount of amine oxide groups
present in the polyamine oxide polymer can be ~aried by
appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide is
from 3:l to l:lOOOOOO. The polymers of the present invention
actually encompass random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is
an N-oxide or not. ~-
The amine oxide unit of the polyamine N-oxides has a pKa < 7-
lO, preferably pKa < 7, more preferred pKa < 6.
The polyamine-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical
provided the material has the desired water-solubility and
dye-suspending power.
Typically, the average molecular weight is within the range
of 500 to lOOO,OOO ; more preferred lOOO to 500,000 ; most
preferred 5000 to 1~0,000.
WO94/1l477 PCT/US93/10543 ~
21~811 6 ` ~
~; The polyamine N-oxides of the present invention are
typically present from 0.01 to 10% , more preferably from 0.05
to 1~, most preferred from 0.05 to 0.5 ~ by weight of the dye
transfer inhibiting composition.
`,j
~3
Metallo catalyst
,
l The preferred usage range of the catalyst in the wash is
3 10-8 molar to 10-3 molar, more preferred 10-6 - 10-4 molar.
The esserltial metallo porphin structure may be visualized as
indlcated 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 drawings, but are actually present as in I.
,,
'i Preferred metallo porphin structures are those substituted
at one or more of the 5, 10, 15 and 20 carbon positions of
Formula I (Meso positions), with a phenyl or pyridyl
substituent selected from the group consisting of
.1 ~
1, ~ (~)n~(A)m ~ ~+~(~)n~(A) m
.~ .
wherein n and m may be 0 or 1; A is selected f-om water-
solubilizing group, e.g., sulfate, sulfonate, phosphate or
carboxylate groups; and B is selected from the group
consisting of Cl-C1o alkyl, C1-C1o polyethoxy alkyl and C~-C1o
hydroxy alkyl.
Preferred molecules are those in which the substituents on
the phenyl or pyridyl groups are selected from the group
consisting of
-CH3, -C2H5~ -~H2CH2CH2SO3-, -CH2--~ and -cH2cH(oH)cH
-SO3.
/ W~94/11477 PCT/US93/10543
2~8Sl ~
. , .
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
~ SD3
ijj
This preferred compound is known as metallo tetrasulfonated
tetraphenylporphin. The symbol Xl is (--CY-) wherein each Y,
independently, is hydrogen, chlorine, bromine, fluorine or
meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or
~ heteroaryl.
.~ ~
i The symbol x2 of Formula I represents an anion, preferably
OH- or Cl-. The compound of Formula I may be substituted at
one or more of the remaining carbon positions with C1-Clo
alkyl, hydroxyalkyl or oxyalkyl groups.
tI)
Porphin derivatives also include chlorophyls, chlorines,
i.e. isobacterio chlorines and bacteriochlorines.
Metallo porphyrin and water-soluble or water-dispersable`
derivatives thereof have a structure given in formula II. ~,
! ~ I
X X
~1 X~ X
~ X ~ tII)
,
1~ :
, WO9~ 77 PCT~US93/10~43 `;j
,, 2 ~ 4 y) 8 ~
j where X can be al~yl, alkyl carboxy, alkyl hydroxyl, vinyl,
alkenyl, alkyl sulfate, alkylsulfonate, sulfate, sulfonate,
aryl.
~, The symbol x2 of Formula II represents an anion, preferably
1 o~~ or Cl-.
The symbol X can be alkyl, alkylcarboxy, alkylhydroxyl,
vinyl, alkenyl, alkylsulfate, alkylsulfonate, sulfate,
sulfonate.
Metallo phthalocyanine and derivatives have the structure
indicated in Formula III, wherein the atom positions of the
phthalocyanine structure are numbered conventionally. The
I anionic groups in the above structures contain cations
selected from the ~roup consisting of sodium and potassium
i cations or other non-interfering cations which leave the
structures water-soluble. Preferred phthalocyanine
1 derivatives are metallo phthalocyanine trisulfonate and
¦ metallo phthalocyanine tetrasulfonate.
~ 2 ~ ~ 4
¦ 20 N ~e 6
I 15
~III)
Another form of substitution possible for the present
invention is substitution of the central metal by Fe, Mn, Co
Rh, Cr, Ru, Mo or othex 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 choose
compounds which are available or can be readily synthesized.
~WO94/1~477 21 ~ 8811 PCTtUS93/10~43
L'
;, 9
Beyond 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
compoun~ for the surface. Thus, strongly negatively charged
substituted compounds, for instance the tetrasulfonated
porphin, may be repelled by negatively charged stained
surfaces and are thexefore most likely not to cause attack on
fixed dyes, whereas the cationic or zwitterionic compounds may
be attracted to, or at least not repelled by such stained
surfaces.
An efficient amount of bleaching agent
The dye transfer inhibiting compositions according to the
present invention comprise an efficient amount of bleaching
agent.
According to the present invention, an efficient amount of
bleach is by definition the necessary amount of bleach which
combined with a bleach catalyst leads to a level of dye
oxidation which is between 40~ to 100%, preferably 40% to 60%,
more preferred 60~ to 80~, most pre~erred 80%-100% of the
maximum (Z) per cent of dye oxidation that can be achieved
under the most optimaL conditions ~etermined by those skilled
in the art.
The bleaches suitable for the present invention can be
activated or non-activated bleaches.
Preferably, the bleaches suitable for the present inventlon
include peroxygen bleaches. Examples of suitable water-soluble
solid peroxygen bleaches incIude hydrogen peroxide releasing
agents such as hydrogen peroxide, perborates, e.g. perborate
monohydrate, perborate tetrahydrate, persulfates,
percarbonates, peroxydisulfates, perphosphates and
W094/l1477 P~CT/US93/10543
~,
peroxyhydrates. Preferred bleaches are percarbonates and
perborates.
~ '.
The hydrogen peroxide releasing agents can be used in
con~ination with bleach activators such as
tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate
(NOBS, described in US 4,412,934),3,5,5-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP
j 120,591), or pentaacetylglucose (PAG), which are perhydrolyzed
¦ to form a peracid as the active bleaching species, leading to
improved bleaching effect.
The hydrogen peroxide may also be present by adding an
enzymatic system 5i.e. an enzyme and a substrate therefore)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process. Such
enzymatic systems are disclosed in EP Patent Application
91202655.6 filed October 9, 1991.
Other peroxygen bleaches suitable for the present invention
include organic peroxyacids such as percarboxylic acids.
Test MQth~ds:
For a given catalyst concentration, temperature and pH, the
following two test methods can be u_~d to estimate the optimum
bleach level that gives the maximum level of dye oxidation,
i.e. Z.
(a) In solution dye bleachin~:
, : .
In a detergent solution, fix the initial concentration of
dye (e.g. 40 ppm) and catalyst. Record the absorbance
spectrum of this solution using a W-Vis spectrophotometer
according to procedures known to those skilled in the art.
Add a given concentxation of bleach (H202, oxone,
percarbonate, perborate, activated bleach, etc..) and stir the
solution containing the dye and catalyst. After stirring for
.
, WOU4/11477 - ~ ,, 8 8 1 1 ~
`. 1 1
, 30 min, record again the absorbance spectrum of the solution.
The amount of dye oxidation can then be determined from the
change in the absorbance maximum for the dye. Keeping the
experimental conditions the same, vary the amount of bleach so
~l as to achieve the maximu-n dye oxidation.
~;1
:'3
~b, ~b) Reduction of dye txansfer from fabric to another fabric
In either a washing machine or launderometer, add a known
bleeding fabric and a known uncolored pick-up tracer (e.g.
cotton~ to the wash load. After simulating a wash cycle,
determine the amount of dye that has been picked up by the
tracer according to methods known to those skilled in the art.
Now to separate washing machines, add the same amount of
bleeding fabric and pick-up tracer, a fixed amount of catalyst
and vary the bleach level. Determine the level of dye
transfer onto the pick-up tracers and vary the amount of
bleach as to minimize dye transfer. In this way the most
optimal bleach concentration can be determined.
I
DETERGENT ADJUNCTS
A wide range of surfactants can be used in the detergent
compositions. A typical listing of anionic, nonionic,
!~ ampholytic and zwitterionic classes, and species of these
'l surfactants, is given in US Patent ~,664,961 issued to Norris
! on May 23, 1972.
! Mixtures of anionic surfactants are particularly suitable
~, ~ herein, especially mixtures of sulphonate and sulphate
3 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, especially 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-Clg fatty source preferably from a
l6-C18 fatty source. In each instance ~he catlon is an
alkali metal, preferably sodium. Preferred sulphate
~ WO94/11477 ~ PCr/US93/10;43 ;~
; 214~811 ;i
12
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, coconut alkyl sulphate, and
C~ s 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 provi.de a surfactant having an average hydrophilic-
lipophilic balance ~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 group which is
I condensed with any particular hydrophobic group can be readily
adjusted to yield a water-soluble compound having the desired
degree of balance between hydrophilic and hydrophobic
elements.
I Especially preferred nonionic surfactants of this type are
the Cg-C1s primary alcohol ethoxylates containing 3-8 moles of
ethylene oxide per mole of alcohol, particularly the C14-C1s
primary alcohols containing 6-8 moles of ethylene oxide per
mole of alcohol and the C12 C14 primary alcohols containing 3-
5 moles of ethylene oxide per mole of alcohol.
.
Another class 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 from 12 to 18 carbon ~ r.
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4,
the compounds including less than 10~ unreacted fatty alcohol i;
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.
.
W~ 477 PCT/US93/10543
13
Also suitable as nonionic surfactants are poly hydroxy fatty
acid amide surfactants of the formula
.'
I R2 - C - N - Z,
O
wherein R1 is H, or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl or a mixture thereof, R2 is Cs_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl haviny a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected
to the chain, or an alkoxylated derivative thereof.
Preferably, R1 is methyl, R2 is a straight C~ s alkyl or
alkenyl chain such as coconut alkyl or mixtures thereof, and Z
is derived from a reducing sugar such as glucose, fructose,
maltose, lactose, in a reductive amination reaction.
The compositions according to the present 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 ethylenediamine tetraacetate, metal ion
sequestrants such as aminopolyphosphonates, particularly
ethylenediamine tetramethylene phosphonic acid and diethylene
triamine pentamethylenephosphonic acid. Though less preferred
for obvious environmental reasons, phosphate 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 (Na2Si2Os).
Suitable polycarboxylates builders for use herein include
citric acid, preferably in the form of a water-soluble saltt
derivatives of succinic acid of the formula R-
CH~CoOHjCH2(COOH) whereln R is C10-20 alkyl or alkenyl,
i
'
~ WO94/11477 ` 21~881~ PCT/~593/1054~ :
` :
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-dodecenylsuccinate, 2-tetradecenyl
succinate. Succinate builders are preferably used in the form
of their water-soluble 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 well as the corresponding soaps.
Preferred saturated species have from 12 to 16 carbon atoms
, in the alkyl chain. The prefe~red unsatur~ated fatty acid ls
j ole.ic acid.
Preferred builder systems for use in granular compositions
include a mixture of a water-insoluble aluminosilicate builder
¦ such as zeolite A, and a watersoluble carboxylate chelating
agent such as citric acid.
' Other builder materials that can form part of the buildex
i system for use in granular compositions the purposes of the
¦ invention include inorganic materials such as alkali metal
i carbonates, bicarbonates, silicates, and organic materials
~ such as the organic phosphonates, amiono polyalkylene
I phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or
co-polymeric acids or their salts, in which the polycarboxylic
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-1,5g6,756.
Examples of such salts axe polyacrylates of MW 2000-5000 and
their copolymers with maleic anhydride, such copolymers having 1
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 usually from 30% to 60% by weight.
WO94/11477 PCT/VS93/10543 1-
Other components used in detergent compositions may be
employed, such as bleaches, suds boosting or depressing
agents, enzymes and stabilizers or activators therefor, soil-
suspending agents soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents,
and perfumes.
Especially preferred are combinations with technologies which
also provide a type of color care benefit. Examples of these
technologies are polyvinylpyrrolidone polymers and other
polymers which have dye transfer inhibiting properties.
Another example of said technologies are cellulase for color
maintenance/ rejuvenation.
Other examples are polymers disclosed in EP 92870017.8 filed
January 31, 1992 and enzyme oxidation scavengers dis~losed in
~P 92870018.6 filed January 31, 1992. also particularly
suitable are amine base catalyst stabilizers disclosed in EP
92870019.4 filed January 31, 1992.
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
conventional granular detergents, i.e. from 550 to 950 g/l; in
suc~ case, the granular detergent compositions according to
the present invention will contain a lower amount of
"inorganic filler salt", compared to conventional granular
detergents; typical filler salts are alkaline earth m~tal
salts of sulphates and chlorides, typically sodium sulphate;
"compact" detergents typically comprise not more than 10%
filler salt. The liqùid compositions according to the present
invention can also be in "compact form", in such case, the
liquid detergent compositions according to the present t
invention will contain ~a lower amount of water,compared to
conventional liquid detergents.
The present in~ention also relates to a process for
inhibiting dye transfer from one fabric to another of
~WO94~11477 PCTtUS93/]OS43 ~
21~8811 i-;`;`
- ` 16
solubilized and suspended dyes encountered during fabric
laundering operations involving colored fabrics.
IThe process comprises contacting fabrics with a laundering
jsolution 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 75 C, especially 20 ~o 60,
but the pol~mers are effecti~e at up to 95 C. The pH of the
treatment solution ls preferably from 7 to 11, especially from
7.5 to 10.5.
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 necessarily meant to
Ilimit or otherwise define the scope of the invention, said
scope being determined according to claims which follow.
Example I
The extent of dye transfer from different colored fabrics
was studied using a launder-o-meter test which simulates a 30
min wash cycle. The launder-o-meter beaker contains 200 ml of
a detergent solution (pH 7.5- 10.5), a l~xlO cm piece of the
colored fabric and a multi-fiber swatch which is used as a
pick-up tracer for the bleeding d~e. The multifiber swatch
consists of 6 strips (1.5cmx1.5cm each~ made of different
materials (polyacetate, cotton, polyamide, polyester, wool and
orlon) which were sewn together.
The extent of dye transfer is reported in terms of the c
value which represents the change in the Hunter a, b values
and is defined by the following equation:
~ C - {(af ~ai)2 + (bf-bi)2}l/2
where the subscripts i and f refer to the Hunter value before
and after washing in the presence of the bleeding fa~ric,
respectively.
WO94/11477 17 ,?l PCI/US93/10543 ~`
Exarnple I ~a): poly(4-vinylpyridine-N-oxide) and FeTPPS
'~ I
The experimental conditions are:
A:detergent solution without any dye transfer inhibition
system.
`I B:detergent solution containing 10 ppm of Iron-
J tetrasulfonated phenylporphyrin ~FeTPPS) and the optimum
! level of bleach as determined from the test method above.
C:deter~ent solution containing 10 ppm of poly(4-
vinylpyridine-N-oxide)(PVNO).
D:detergent solution containing 10 ppm of FeTPPS and 10 ppm of
poly(4-vinylpyridine~N-oxide).
)
i ~ C value on cotton
Fabric A B ~ C D
~ ~, ~
blue sweater 15.2 14.7 8.2 4.8
purple trousexs-1 19.3 7.0 17.8 2.8
green sweater 8.7 8.4 6.6 4.5
purple ~ogging 12.7 12.2 7.6 5.7
purple trousers 14.5 13.1 6.4 4,3
blue trousers 18.7 13.9 22.2 10.8
The higher the ~ C value, the more dye transferred onto the
pick-up swatch.
Conclusion: The dye transfex inhibition benefits from the
combined PVNO and FeTPPS are in all cases better than
benefits provided by either the catalyst or polymer alone. In
addition, not only additive effects are observed but these
results show true synergism between the catalyst and poly~4-
vinylpyridine~N-oxidel.
I WO94/11477 PCT/US93/10543
'-'21~8811
18
~xample I(b): poly(4-vinylpyridine-N-oxide) and MnPc
The experimental conditions are:
A:detergent solution without any dye transfer inhibition
system.
B:detergent solution containing 10 ppm of Mn-Phthalocyanine
tetrasulfonated ~MnPC) and the optimum level of bleach as
determined from the test method above.
C:detergent solution containing 10 ppm of poly(4-
vinylpyxidine-N-oxide). (PVNO)
D:detergent solution containing 10 ppm of MnPc ~nd 10 ppm of
poly(4-vinylpyridine-N-oxide).
~C values on cotton
_ __
Fabric A B C D
blue sweater 15.214.7 8.2 4.8
green sweater 8.7 8.4 6.6 4.5
purple jogging 12.712.2 7.6 5.7
purple trousers 14.513.1 6.4 4.3
Concluslon: The dye transfer inhibition benefits from the
combined PVNO and MnPC are in all cases better than benefits
provided by either the catalyst or polymer alone. In
addition, these results show true synergism between the
catalyst and poly(4-vinylpyridine-N-oxide).
. ~ ." ,, , . .... ..... ... ... .. . -
~ WO94/11477 PCT/US93/10~43
,21~`8811
~I
`~ EXAMPLE II (A/B/C/D)
.
, A liquid dye transfer inhibiting composition according to the
present invention is prepared, having the following
'~ compositions :
~i!
.,
- ~inear alkyl benzene sulfonate 10
- Sodium C12_15 alkyl sulfate 3
- C14_1s alkyl 2.5 times ethoxylated sulfate 0
- C12 glucose amide 0
- C12_1s alcohol 7 times ethoxylated 11.6
- Oleic acid 2.5
- Citric acid
- C12_14 alkenyl substituted succinic acid 0
- Sodium Hydroxide 3.5
- Ethanol 6
- Monoethanolamine 0
- Triethanolamine 6.4
- 1,2-propane diol 1.5
- Glycerol o
- Boric acid o
- Diethylene triamine penta 0.8
(methylene phosphonic acid)
- CaC12
- Soil release polymers 0.5
- Fatty acids 12
- Enzymes 0.65
Water and minors - - - - Balance to 100% - - -
The above composition was supplemented with the catalyst,
p~lymer and bleach accordlng to table I
WO94/11477 PCT/US93/10~3 ~
2~8811 20
Table I
A B C D
..
- Catalyst l: Mn-tetrasulfonated 0 0.05 0 0
tetraphenylporphine
- Catalyst 2: Cr-tetrasulfonated 0 0 O.lO0 0
tetraphenylporphine
- Catalyst 3: Fe tetrasulfonated 0 0 0 0.2
tetraphenylporphine
- Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0
tetrasulfonated
~ H22 0.3-0~5 0 0 0
- Perborate 0 0 1-5 0.5
- Percarbonate , 0 0.4 0 O.lO0-
Pc~ly(4-vinylpyridine-N-oxide) O.l 0.30.05 0.2
- TAED 0 O 0 5 0
Example III ~A/B/C/D):
A compact granular dye transfer inhibiting composition
according to the present invention is prepared, having the
followir1g formulation:
%
Linear alkyl benzene sulphonate ll.40
Tallow alkyl sulphate l.80
C4s alkyl sulphate 3.00
C~s alcohol 7 times ethoxylated 4.00
Tallow alcohol ll times ethoxylated l.80
Dispersant ` ~ 0.07
Silicone fluid 0.80
Trisodium citrate 14.00
Citric acid 3.00
Zeolite 32.50
Maleic acid actylic acid copolymer 5.00
DETMPA : l.00
Cellulase (active protein) 0.03
W094/11477 PCT/US93/l0543
21
Alkalase/BAN 0.60
Lipase 0.36
Sodi.um silicate 2.00
Sodium sulphate 3.50
Minors up to 100
The above composition was supplemented with the catalyst,
polymer and bleach according to table II
Table II
A B C D
- Catalyst 1: Mn-tetrasulfonated 0 0.05 0 0
tetraphenylporphine
- Catalyst 2: Cr-tetrasulfonated 0 0 0.100 0
tetraphenylporphine
- Catalyst 3: Fe-tetrasulfonated 0 0 0 0.2
tetraphenylporphine
- Catalyst 4: Mn-Phthalocyanine 0.15 0.0 0 0
tetrasulfonated
~ H22 0.3-0.5 0 0 0
Perborate 0 0 1-5 2.5
- Percarb,onate 0 0.4 0 0
- Poly(4-vinylpyridine-N-oxide) 0.050.1 0.15 0~2-0.4
- TAED 0 0 0.5 1.0
.
