Note: Descriptions are shown in the official language in which they were submitted.
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WO 98/30664 PCT/EP97/07327
DETERGENT COMPOSITIONS AND COPOLYMERS FOR INHIBITING DYE TRANSFER
Technical Field
The present invention relates to a detergent composition and to
a process for inhibiting dye transfer between fabrics during
washing. In particular, the invention relates to detergent
compositions containing novel dye-transfer inhibition
copolymers.
Backaround of the Invention
There is a tendency during the laundering of fabrics for
coloured fabrics to release dye into the wash solution. This
is a most persistent and troublesome problem as this released
dye can then be transferred onto other fabrics. Afabric
treatment composition comprising an agent which could prevent
the transfer of dye would therefore prove useful.
EP462 806 (Unilever) discloses a domestic treatment of a
fabric with a cationic dye fixing agent to reduce the amount
of dye released from the fabric. Suitable cationic dye
fixing agents include the dimethyldiallyl ammonium chloride
polymer.
Surfactant-containing dye transfer inhibiting compositions are
disclosed in EP 0 587 550 (Procter and Gamble). The dye
transfer inhibition agent is a polymer selected from
polyamine N-oxide containing polymers.
EP O 327 927 (Procter and Gamble) describes a granular
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detergent additive comprising water-soluble polymeric
compounds based on N-vinylpyrrolidone and/or N-vinylimidazole
and/or N-vinyloxazolidine and cationic compounds.
Detergent compositions comprising a N-vinylimidazole N-
vinylpyrolidone copolymer are disclosed in EP 0 635 566 and EPo
635 565 (Procter and Gamble).
DE 42 24 762A (BASF AG) discloses the use of nitrogen-
containing polymers as dye-transfer inhibitors in textile
washing, the polymers contain a carbonyl or ester group with
the esters being neutral in the co-polymer.
EP-A-0-631-008 (Ciba-Geigy AG) relates to an after-washing
process for a dyeing operation in which a polyvinyl pyrrolidone
homo or co-polymer, and, a water softener are used in the
absence of a surfactant. The copolymer can contain comonomers
such as those containing carboxyl groups, sulpho groups,
phosphorous based groups or other ethylenically unsaturated
monomers. Such non-surfactant dyeing after washing processes
and compositions used in them are outside the scope of the
present invention.
EP-0-100-890-A (BASF AG) discloses co-polymers obtained by the
radical copolymerisation of monomers of C3-C2o alkyl ester of
(meth)acrylic acid N-containing neutrally reacting water-
soluble compounds, compounds containing cationic groups and
olefinically unsaturated Cj-CS carboxylic acids. The polymers
are used in hair treatment compositions.
.. __._... .. . _ . _.__-.
r ~. ~-.-..~._.~.... . ..
' CA 02277484 1999-07-09
Document #: 344111
C3757 3
WO 95/27759 discloses ink compositions comprising network forming
or cross-linked polymers or resins, where the polymers may
include a dye-binding copolymer.
EP 687 694 (BASF) discloses a process for the preparation of
polymers base on vinyl imidazoles. The process relates to vinyl
imidazole co-polymers and homopolymers.
WO 91 00302 (GAF) discloses terpolymers which are insoluble in
heptane and which are produced form a reaction mixture of a vinyl
lactam, a polymersible carboxylic acid and a hydrophobic monomer.
WO 95/00611 discloses floor cleaners comprising a copolymer of
vinyl pyrrolidone and acrylic acid, dimethylaminoethyl
methacrylate, vinyl acetate or methaminopropyl trimethyl ammonium
chloride. The copolymers are used as shine boosters.
We have found that whilst these polymers of the prior art when
used for dye transfer mitigation can be effective in preventing
dye transfer under model conditions, in the presence of soil under
normal laundering conditions they become ineffective, and can even
lead to additional dye transfer.
Compositions of the present invention are directed towards
overcoming this problem by using co-polymers which even in the
presence of soil, retain their dye transfer inhibition properties.
Definition of the Invention
Accordingly the present invention provides a fabric wash
detergent composition comprising a co-polymer and at least one
.'C::.,~~1~'~ ~~ c
I~I=wcP
CA 02277484 1999-07-09
C3757
component selected from surface active agents and fabric
softening compounds, the co-polymer comprising at least one dye
binding monomer selected from vinyl azalactam monomers, vinyl
azalactone monomers, vinyl pyridine, vinyl pyridine-N-oxide,
vinyl oxazolidone or mixtures thereof and at least one monomer
selected from anionic monomers and ethylenically unsaturated
polyethylene glycol derivatives, with the proviso that the co-
polymer is not poly(1-vinylpyrrolidone-co-acrylic acid).
Of particular interest are dye binding co-polymers of
poly(vinylpyrrolidone-co-polyvinylimidazole-co-acrylic acid) or
a co-polymer of poly(vinylpyrrolidone-co-polyvinylimidazole-co-
methacrylic acid) or a co-polymer of poly(vinylpyrrolidone-co-
polymethylvinylimidazole-co-acrylic acid) or a co-polymer of
poly(vinylpyrrolidone-co-polymethylvinylimidazole-co-
methacrylic acid).
The invention also relates to use of a co-polymer comprising at
least one dye binding monomer selected from vinyl azalactone,
vinyl azalactam monomers, vinyl pyridine, vinyl pyridine-N-
oxide, vinyl oxazolidone or mixtures thereof, and at least one
monomer selected from anionic monomers and ethylenically
unsaturated polyethylene glycol derivatives, in a laundry
treatment composition to mitigate dye transfer between fabrics.
The present invention further provides use of a co-polymer
comprising at least one dye binding monomer selected from vinyl
azalactone monomers, vinyl azalactam monomers, vinyl pyridine,
vinyl pyridine-N-oxide, vinyl oxazolidone or mixtures thereof,
and at least one monomer selected from anionic monomers and
ethylenically unsaturated polyethylene glycol derivatives, to
prevent redeposition of soil in fabric washing conditions.
r~ ~~, -» .~.-T
~; '.~~i:. :'~...,.._.... .-;'yes
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C3757 ' S -
In particular co-polymers as defined above comprising 1-10% by
weight acrylic acid or methacrylic acid monomers are of use.
The teen dye-binding monomer as used herein is used in relation
to monomers which have a dye-binding capability when in their
polymerised form i.e. the co-polymer comprising the polymerised
dye-binding monomers has dye binding characteristics resulting
from said monomer.
More specifically in the context of the present invention a dye
binding monomer is defined as a monomer the homopolymer (mwt of
40,000-100,000) of which binds dye in water at pH at a
temperature from 5°C to 60°C, preferably at a temperature of
20°C. However, with this proviso the dye binding homopolymer
can bind dye under other conditions.
Detailed Description of the Invention
The copolymers of the invention at least one dye binding
monomer and at least one anionic or nonionic monomer.
Preferred polymers include vinyl pyrrolidone (VP), vinyl
imidazole (VI), methyl vinyl imidazole (MeVI), vinyl pyridine,
vinyl pyridine-N-oxide (VPy-N-0), vinyl oxazolidone.
i ;: :. ._ ~. -
i ~ w ,~.- ,; ;._ r
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Especially preferred are vinyl imidazole, methyl vinyl
imidazole (meVI) and vinyl pyridine-N-oxide, used alone or in
combination with vinyl pyrrolidone and combinations thereof.
Any anionic monomer is suitable for use with the invention.
However it is preferred if the anionic moiety is based on a
carboxy, sulphonate, sulphate, phosphate or phosponate
containing material, especially preferred are short chain,
polyTnerisable group carboxy containing material having at
least one double bond. Preferred anionic monomers are
itaconic acid, aconitic acid, mesaconic acid, citraconic
acid, acrylic acid (AA), methacrylic acid (MA), octanoic acid,
hexanoic acid, vinyl acetic acid, vinyl benzoic acid, vinyl
sulphonic acid, vinyl benzene sulphonic acid, vinyl phosphoric
acid and hydroxy acrylic oracetic acid. Especially preferred
are AA, MA and vinyl sulphonic acid
Examples of preferred copolymers are described below.
i ) ~~_ ~ ~~~~~y ( ii~~
CO~bI COibl N~ O
p R~ ~~~.Rn
N ~N
~( CA~1 PAY( ~)
~CH~-~~CH~.CH-~-~CH=.CH~ "~"Ctl:_CRn~CHz.CH~
x r
(iii) ~~ N ( Z O (iv) ~iM y
~W R"
N H
Poh(MIWwPI i
O
~h( cNPY-~1
M ~ H) l~l~', K', IdH,
CAS Carboxylic acid. X,Z,Z is the polmerisation number so
. R = H, A1 mwt is achieved.
kyl; ~g Clip, CsH~, ate; n ~ t-4 inaependentaly of each other
Y
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C3757
For (ii) it is preferred that R' is H so that the polymer is
poly(acrylic acid/VI/VP). It is possible that VI may have R'
as CH3 i.e. be methyl vinyl imidazole which is another
preferred co-polymer. This applies for each of (i)-(iii)
above.
The weight ratio of anionic or nonionic monomertsa to the dye
- binding monomers) within the co-polymer is preferably from 1:200
to 1:1, more preferably 1:15J to 1:2, most preferably 1:100 to
1:3.
It may be desirable to include additional monomers in these
dye binding polymer. Examples of these additional monomers
include vinyl alcohol, vinyl acetate, vinyl styrene, acrylamide,
methyl methacrylate, hydroxyethyl acrylate/methacrylate, IEG
acrylate/methacrylate, glycidyl acrylate/methacrylate. The
addition of these third monomers can cause changes in the
properties of these polymers such as solubility, compatibility
with liquid products and redeposition performance or
sequestration ability. However, such further monomers may be
.. _. , -. . ' ._. ~... .
';, '. : ,_
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included if the properties of the co-polymers are not adversely
affected.
Additional monomers may also be present for cost
minimalisation) as a cross-linking moiety or to impart
biodegradability. However, non-crosslinked co-polymers are
preferred. The co-polymers of the present invention most
preferably retain the anionic ar nonionic nature of the
monomers within the co-polymer.
It is preferred if the co-polymer has an average molecular weight
range from 2,000 to 200,000 more preferably from 5,000 to 100.000, most
If the detergent composition is in liquid forth it is
preferred if the co-polymer has a molecular weight range from
5,000 to 30,000. If the detergent composition is granular the
preferred molecular weight is from 10,000 to 50,000.
The detergent compositions may comprise 0.001-5% w/w of the
copolymer, preferably 0.1-3%, e.g. 0.1-2%, such as 0.1-1%.
In the context of the present invention the most preferred
co-polymers are selected from the group consisting of:
a) co-polymers of PVP/PVI/AA, PVP/PVI/MA especially where the
ratio of PVI/PVP is from 2:1 to 0.2:1, most preferably 1:1 to
0.3:1
b) co-polymers of PVI/AA, PVI/MA and:
c) co-polymers of PVPy-N-O/AA, PVPy-N-0/MA.
d) co-polymers of PVP/MePVI/AA, PVP/MePVI/MA especially where the
weight ratio of PVP:PVI/MePVI is from 90:10 to 10:90, especially
75:25 to 25:75, e.g. 50:50.
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Co-polymers comprising at least one dye-binding monomer selected
from VI, MeVI and VP where the anionic monomer is AA are
especially preferred.
The ratio of VP/meVI or VI when two dye binding monomers are used
together is preferably in the weight ratio range stated above in
a) or d) .
It is also advantageous, especially for VP/meVI co-polymers if
the anionic monomer, which is preferably AA or MA represents 1-
10% w/w of the copolymer, especially 2-8%, most especially 2.5%-
7% w/w. Excellent results for both the mitigation of dye
transfer and anti-redeposition have been obtained with VP/meVI
co-polymers containing around 3% MA or AA, particularly when the
ratio of the VP/meVI is within the range 90:10 to 10:90,
preferably 75:25 to 25:75 e.g. 50:50.
In addition to dye transfer inhibition properties the
compositions of the invention also exhibit excellent
redeposition of soil properties. This is especially
advantageous for the co-polymers of VP, with VI or
MeVI, and AA or. MA.
The compositions of the invention comprise a component
selected from surface active agents and fabric
softening compounds. Typically at least one of the
two aforementioned components will be present
dependent upon the application.
The compositions of. the present invention are
preferably laundry compositions, especially main wash
compositions or rinse-added softening compositions.
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The main wash compositions may include a fabric
softening agent.
Surface Active Compounds
The detergent compositions of the invention may
contain a surface-active compound (surfactant) which
may be chosen from soap and non-soap anionic,
cationic, nonionic, amphoteric and zwitterionic
surface-active compounds and mixtures thereof. Many
suitable surface-active compounds are available and
are fully described in the literature, for example, in
"Surface-Active Agents and Detergents", Volumes I
and II, by Schwartz, Perry and Berch.
The preferred detergent-active compounds that can be
used are soaps and synthetic non-soap anionic and
nonionic compounds.
It is preferred if the compositions of the invention
contain linear alkylbenzene sulphonate, particularly
linear alkylbenzene sulphonates having an alkyl chain
length of CR-CiS. It is preferred if the level of
alkylbenzene sulphonate is from 0 wt% to 30 wt%, more
preferably 1 wt% to 25 wt%, most preferably from 2 wt%
to 15 wt%.
The detergent compositions of the invention may contain other
anionic surfactants in amounts additional to the percentages
quoted above. Suitable anionic surfactants are well-known to
those skilled in the art. Examples include primary and
secondary alkyl sulphates, particularly Cg-C,5 primary alkyl
r T _.__ ._...__... T ._..____m_._~..
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sulphates; alkyl ether sulphates; olefin sulphonates; alkyl
xylene sulphonates; dialkyl sulphosuccinates; and fatty acid
ester sulphonates. Sodium salts are generally preferred.
The compositions of the invention may also contain nonionic
surfactant. Nonionic surfactants that may be used include the
primary and secondary alcohol ethoxylates, especially the cec,,)
aliphatic alcohols ethoxylated with an average of from 1 to 20
moles of ethylene oxide per mole of alcohol, and more
especially the C,o-C,5 primary and secondary aliphatic alcohols
ethoxylated
with an average of from 1 to 10 moles of ethylene oxide per
mole of alcohol. Non-ethoxylated nonionic surfactants
include alkylpolyglycosides, glycerol monoethers, and
polyhydroxyamides (glucamide).
It is preferred if the level of nonionic surfactant is from 0
wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably
from 2 wt% to 15 wt%.
The choice of surface-active compound (surfactant), and the
amount present, will depend on the intended use of the
detergent composition. In fabric washing compositions)
different surfactant systems may be chosen, as is well known
to the skilled formulator, for handwashing products and for
products intended for use in different types of washing
machine.
The total amount of surfactant present will also depend on
the intended end use and may be as high as 60 wt%, for
example, in a composition for washing fabrics by hand. In
compositions for machine washing of fabrics, an amount of
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from 5 to 40 wt% is generally appropriate. Typically the
compositions will comprise at least 2 wts surfactant e.g. 2-
60a, preferably 15-40°s most preferably 5-35%.
Detergent compositions suitable for use in most automatic
fabric washing machines generally contain anionic non-soap
surfactant, or nonionic surfactant, or combinations of the
two in any ratio, optionally together with soap.
Fabric Softening Compounds
Any conventional fabric softening compound may be used in the
compositions of the present invention. The softening
compounds may be cationic or nonionic. If the fabric softening
compound is to be employed in a main wash detergent composition
the compound will typically be nonionic.
The fabric softening compound is suitably a substantially water
insoluble quaternary ammonium material comprising a single
alkyl or alkenyl long chain having an average chain length
greater than or equal to CZO or, more preferably, a compound
comprising a polar head group and two alkyl or alkenyl chains
having an average chain length greater than or equal to C14.
Preferably the fabric softening compound has two long chain
alkyl or alkenyl chains each having an average chain length
greater than or equal to C16. Most preferably at least 50~ of
the long chain alkyl or alkenyl groups have a chain length of
Cle or above
It is preferred if the long chain alkyl or alkenyl groups of
the fabric softening compound are predominantly linear.
___._.~._..__.__...r.__~__.......
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The fabric softening compounds used in the compositions of the
invention are preferably compounds that provide excellent
softening, and characterised by a chain melting L beta to L
alpha transition temperature greater than 25°C, preferably
greater than 35°C, most preferably greater than 45°C. This L
beta to L alpha transition can be measured by DSC as defined in
" Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton,
Florida, 1990 (pages 137 and 337).
Substantially insoluble fabric softening compounds in the
context of this invention are defined as fabric softening
compounds having a solubility less than 1 x10 3 wt % in
deminerailised water at 20°C. Preferably the fabric softening
compounds have a solubility less than 1 x10-' wt %. Most
preferably the fabric softening compounds have a solubility
less than 1 x10 8 to 1 x10 6.
Preferred fabric softening compounds are quaternary ammonium
compounds. It is especially preferred if the fabric softening
compound is a water insoluble quaternary ammonium material
which comprises a compound having two C12-le alkyl or alkenyl
groups connected to the molecule via at least one ester link.
It is preferred if the quaternary ammonium material has two
ester links present. An especially preferred ester-linked
quaternary ammonium material can be represented by the formula;
Rt
R1 N (CHZ) ~-T-Rz
(CHZ) n-T_R2
i
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wherein each R1 group is independently selected from C1_4 alkyl,
hydroxyalkyl or C2_4 alkenyl groups; and wherein each R2 group
is independently selected from CB_28 alkyl or alkenyl groups;
O O
T is -O-C- or -C-O-; and N is an integer from 0-5.
Di (tallowowyloxyethyl) dimethyl ammonium chloride is
especially preferred.
A second preferred type of quaternary ammonium material can be
represented by the formula;
OOCR2
(R~ ) 3N - (CHz) n CH
CHZOOCRz
wherein Rl ( n and RZ are as defined above .
It is advantageous if the quaternary ammonium material is
biologically biodegradable.
Preferred materials of this class such as 1,2 bis (hardened
tallowoyloxy) -3- trimethylamQnonium propane chloride and their
method of preparation are, for example, described in US 4 137
180 (lever Brothers). Preferably these materials comprise
small amounts of the corresponding monoester as described in US
4 137 180 for example 1- hardened tallowoyloxy-2-hydroxy-3-
trimethylammonium propane chloride.
Lecithins are also suitable softening compounds.
_..__.~s..~_~__~.__..__....
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DeterQencv Builders
The detergent compositions of the invention will generally
also contain one or more detergency builders if they are for
use in the main wash of a laundering process. The total
amount of detergency builder in the compositions will typically
suitably range from 5 to 80 wt%, preferably from 10 to
60 wt%.
Inorganic builders that may be present include sodium
carbonate, if desired in combination with a crystallisation
seed for calcium carbonate, as disclosed in GB 1 437 950
(Unilever); crystalline and amorphous aluminosilicates) for
example, zeolites as disclosed in GH 1 473 201 (Henkel),
amorphous aluminosilicates as disclosed in GB 1 473 202
(Henkel) and mixed crystalline/amorphous aluminosilicates as
disclosed in GB 1 470 250 (Procter & Gamble); and layered
silicates as disclosed in EP 164 5148 (Hoechst). Inorganic
phosphate builders, for example, sodium orthophosphate,
pyrophosphate and tripolyphosphate are also suitable for use
with this invention.
The detergent compositions of the invention preferably
contain an alkali metal, preferably sodium, aluminosilicate
builder. Sodium aluminosilicates may generally be incorporated
in amounts of from 10 to 70% by weight (anhydrous basis),
preferably from 25 to 50 wt%.
The alkali metal aluminosilicate may be either crystalline or
amorphous or mixtures thereof, having the general formula:
0 . 8 -1 . 5 NazO . A1203 . 0 . 8 - 6 S i02
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These materials contain some bound water and are required to
have a calcium ion exchange capacity of at least 50 mg Ca0/g.
The preferred sodium aluminosilicates contain 1.5-3.5 Si02
units (in the formula above). Both the amorphous and the
crystalline materials can be prepared readily by reaction
between sodium silicate and sodium aluminate, as amply
described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange
detergency builders are described, for example, in
GB 1 429 143 (Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known commercially
available zeolites A and X, and mixtures thereof.
The zeolite may be the cocrnnercially available zeolite ~A now
widely used in laundry detergent powders. However, according
to a preferred embodiment of the invention, the zeolite
builder incorporated in the compositions of the invention is
maximum aluminium zeolite P (zeolite M,~P>as described and
claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as
an alkali metal aluminosilicate of the zeolite P type having
a silicon to aluminium ratio not exceeding 1.33) preferably
within the range of from 0.90 to 1.33, and more preferably
within the range of from 0.90 to 1.20.
Especially preferred is zeolite M~ having a silicon to
aluminium ratio not exceeding 1.07.more preferably about
1.00. The calcium binding capacity of zeolite MAPis
generally at least 150 mg Ca0 per g of anhydrous material.
Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers,
._ _~_.-.~._-..,..
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and acrylic phosphinates; monomeric polycarboxylates such as
citrates, gluconates, oxydisuccinates, glycerol mono-, di
and trisuccinates, carboxymethyloxysuccinates,
carboxymethyloxymalonates,dipicolinates,hydroxyethyiiminodiacet
ates, alkyl- and alkenylmalonates and succinates; and
sulphonated fatty acid salts. This list is not intended to be
exhaustive.
Especially preferred organic builders are citrates, suitably
used in amounts of from 5 to 30 wt%, preferably from 10 to 25
wt%; and acrylic polymers, more especially acrylic/maleic
copolymers, suitably used in amounts of from 0.5 to 15 wt%,
preferably from 1 to 10 wt%.
Builders, both inorganic and organic, are preferably present
in alkali metal salt, especially sodium salt, form.
Bleach Components
Detergent compositions according to the invention may also
suitably contain a bleach system..Fabric washing
compositions may desirably contain peroxy bleach compounds,
for example, inorganic persalts or organic peroxyacids,
capable of yielding hydrogen peroxide in aqueous solution.
Suitable peroxy bleach compounds include organic peroxides
such as urea peroxide, and inorganic persalts such as the
alkali metal perborates, percarbonates, perphosphates,
persilicates and persulphates. Preferred inorganic persalts
are sodium perborate monohydrate and tetrahydrate, and sodium
percarbonate.
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Especially preferred is sodium percarbonate having a
protective coating against destabilisation by moisture.
Sodium percarbonate having a protective coating comprising
sodium metaborate and sodium silicate is disclosed in
GB 2 123 044B (Kao).
C3757
The peroxy bleach compound is suitably present in an amount
of from 0.1 to 35 wt%, preferably from 0.5 to 25 wt%.
The peroxy bleach compound may be used in conjunction with a
bleach activator (bleach precursor) to improve bleaching
action at low wash temperatures. The bleach precursor is
suitably present in an amount of from 0.1 to 8 wt%,
preferably from 0.5 to 5 wt%.
Preferred bleach precursors are peroxycarboxylic acid
precursors, more especially peracetic acid precursors and
pernoanoic acid precursors. Especially preferred bleach
precursors suitable for use in the present invention are
N,N,N',N.-tetracetyl ethylenediamine (TAED) and sodium
noanoyloxybenzene sulphonate (SNOBS). The novel quaternary
ammonium and phosphonium bleach precursors disclosed in
US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP
402971A (Unilever), and the cationic bleach precursors
disclosed in EP 284 292A and EP 303 520A (Kao) are also of
interest.
The bleach system can be either supplemented with or replaced
by a peroxyacid. Examples of such peracids can be found in
US 4 686 063 and US 5 397 501 (Unilever).
a preferred example is the imido peroxycarboxylic class of
peracids described in EP A 325 288, EP A 349 940, DE 382 3172
r _._~._ __T..._~_w _. _ .__._.._ ~.
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and EP 325 289. A particularly preferred example is
phtalimido peroxy caproic acid (PAP). Such peracids are
suitably present at 0.1 - 12% preferably 0.5 - 10%.
A bleach stabiliser (heavy metal sequestrant) may also be
present. Suitable bleach stabilisers include ethylenediamine
tetraacetate (EDTA), the polyphosphonates such as bequest
(Trade Mark) and non-phosphate stabilisers such as EDDS
(ethylene diamine di-succinic acid). These Bleach
stabilisers are also useful for stain removal especially in
products containing low levels of bleaching species or no
bleaching species.
An especially preferred bleach system comprises a peroxy
bleach compound (preferably sodium percarbonate optionally
together with a bleach activator), and a transition metal
bleach catalyst as described and claimed in EP 458 397A,
EP 458 398A and EP 509 787A (Unilever).
The Enzyme
The detergent compositions according to the invention may also
contain an enzyme.
Suitable enzymes include the proteases, amylases, cellulases,
oxidases, peroxidases and lipases usable for incorporation in
detergent compositions.
Preferred proteolytic enzymes (proteases) are, catalytically
active protein materials which degrade or alter protein types
of stains when present as in fabric stains in a hydrolysis
reaction. They may be of any suitable origin, such as
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vegetable, animal, bacterial or yeast origin.
Proteolytic enzymes or proteases of various qualities and
origins and having activity in various pH ranges of from 4-12
are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the stabilisins
which are obtained from particular strains of B. subtilis
B. licheniformis, such as the commercially available
subtilisins Maxatase (Trade Mark), as supplied by Gist
Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), as
supplied by Novo Industri A/S, Copenhagen, Denmark.
Particularly suitable is a protease obtained from a strain of
Bacillus having maximum activity throughout the pH range of
8-12, being commercially available, e.g. from Novo Industri
A/S under the registered trade-names Esperase (Trade Mark)
and Savinase (Trade-Mark). The preparation of these and
analogous enzymes is described in GB 1 243 785. Other
commercial proteases are Kazusase (Trade Mark) (obtainable
from Showa-Denko of Japan), Optimase (Trade Mark) (from Miles
Kali-Chemie, Hannover, West Germany), and Superase (Trade
Mark) (obtainable from Pfizer of U.S..a. >.
Detergency enzymes are commonly employed in granular forth in
amounts of from about 0.1 to about 3.0 wt%.
Other ingredients
The compositions of the invention may contain alkali metal,
preferably sodium carbonate, in order to increase detergency
and ease processing. Sodium carbonate may suitably be
present in amounts ranging from 1 to 60 wt%, preferably from
2 to 40 wt%. However, compositions containing little or no
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sodium carbonate are also within the scone of the invention.
Powder flow may be improved by the incorporation of a small
amount of a powder structurant, for example, a fatty acid (or
fatty acid soap), a sugar, an acrylate or acrylate/maleate
copolymer, or sodium silicate.
One preferred powder structurant is fatty acid soap, suitably
present in an amount of from 1 to 5 wt%.
Other materials that may be present in detergent compositions
of the invention include sodium silicate; antiredeposition
agents such as cellulosic polymers; inorganic salts such as
sodium sulphate; lather control agents or lather boosters as
appropriate; proteolytic and lipolytic enzymes; dyes;
coloured speckles; perfumes; foam controllers; fluorescers and
decoupling polymers. This list is not intended to be
exhaustive.
It is advantageous if soil release polymers are present as
they enhance the dye transfer inhibition. Particularly
preferred are soil release polymers based disclosed in
WO 95/32997 A (Rhone Poulenc)), EP 219 048 (BASF))
GB 2 208 515 (Colgate), EP 253 567 (P-.G)
The detergent composition when diluted in the wash liquor
(during a typical wash cycle) will typically give a pH of the
wash liquor from 7 to 10.5 for a main wash detergent.
The detergent components of the present invention may be
incorporated in detergent compositions of all physical types,
for example, powders, liquids, gels and solid bars.
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Detergent compositions of the invention may be prepared by
any suitable method.
Particulate detergent compositions are suitably prepared by
spray-drying a slurry of compatible heat-insensitive
ingredients, and then spraying on or postdosing those
ingredients unsuitable for processing via the slurry.
skilled detergent formulator will have no difficulty in
deciding which ingredients should be included in the slurry
and which should not.
Particulate detergent compositions of the invention preferably
have a bulk density of at least 400 g/1, more preferably at
least 500 g/1.
Especially preferred compositions have bulk densities of at
least 650 g/litre, more preferably at least 700 g/litre.
Such powders may be prepared either by post-tower
densification of spray-dried powder, or by wholly non-tower
methods such as dry mixing and granulation; in both cases a
hiqh-speed mixer/granulator may advantageously be used.
Processes using high-speed mixer/granulators are disclosed, for
example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420
317A (Unilever) .
Liquid detergent compositions can be prepared by admixing the
essential and optional ingredients thereof in any desired
order to provide compositions containing components in the
requisite concentrations. Liquid compositions according to
the present invention can also be in compact form which means
___..~. ..._~. T ~..-.... T
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it will contain a lower level of water compared to a
conventional liquid detergent.
Examples
The invention will now be illustrated by the following non-
limiting examples. In the examples all percentages are
expressed by weight. Further modifications within the scope of
the present invention will be obvious to the skilled man.
Comparative Examples are designated by letters, while
Examples of the invention are designated by numbers.
Preparation of Polymers
The co-polymers of this invention can be produced by radical
polymerisation of the appropriate monomers with or without a
crosslinking agent. The polymerisation can be conducted in
bulk, in solution (aqueous or organic media) also employing
emulsion or suspension polymerisation techniques. Depending
on the monomer reactivity ratios and their concentration, the
co-polymers will have random or block nature.
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Example 1
Co-polymerisation of Vinylimidazole & Acrylic Acid (95:5)
1-Vinylimidazole 47g (0.5 mol)
Acrylic Acid 1.8g(25 mol)
1,4-Dioxane 250 ml
4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.148
The radical polymerisation of 1-Vinylimidazole (0.5 mol) and
Acrylic Acid was carried out under nitrogen. After degassing
for 30 minutes, the reaction mixture was heated to 70°C and
ACVA (0.5 mol) was added. The polymerisation reaction was
stirred overnight under a nitrogen atmosphere until the
reaction mixture turned cloudy.
The bulk of the dioxane was removed and sodium hydroxide
solution was added to neutralise the acrylic acid. The
remaining dioxane/water was removed, the sample was
redissolved in water and freeze dried.
NMR Analysis indicate that the co-polymer contains between
4-80 of acrylic acid monomer. GPC Molecular weights against
polyethylene glycol standards are: Mn 40970, Mw 137900,
D3.366.
....___.._ ..... _T_._.. _. ~_....___. . ...
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Example 2
Co-Polymerisation of Vinylimidazole & Acrylic Acid (50:50)
1-Vinylimidazole 18.88 (0.2 mol)
Acrylic Acid 14.4g (0.2 mol)
1,4-Dioxane 300 ml
4,4-Azobis(4-cyanovaleric)acid(ACVA) 0.5g
The polymerisation was carried out as example 1, but with
different monomer ratios. After the polymerisation completed,
sodium hydroxide solution was added to the stirred reaction
product and the polymer precipitated out. The polymer was
redissolved in water and freeze dried or precipitated out
using methanol (three times).
NMR spectrum shows that the copolymer contains about 75
acrylic acid monomer.
Example 3
Co-Polymerlsation of Vinylimidazole ~ Acrylic Acid (80:20)
1-Vinylimidazole 25.8g (0.274
mol)
Acrylic Acid 3.95g(55
mol)
1,4-Dioxane 250 ml
4,4-Azobis(4-cyanovaleric) acid (ACVA) 0.2g
The polymerisation was carried out as example 1, but with
different monomer ratios. After the polymerisation completed,
sodium hydroxide solution was added to the stirred reaction
product and the polymer precipitated out. The polymer was
redissolved in water and freeze dried or precipitated out
using methanol (three times).
NMR analysis indicate that the co-polymer contains about 18
of acrylic acid monomer.
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Dye Transfer Performance
Conditions: Shakerbath, 40°C, 30 rains, 100 rpm
lOOmls solution made with 26.4°FH water
lg/1 total surfactant (combinations of LAS and E07)
0.522g/1 NaC03
0.87g/1 STP
lOuM Direct Red 80 dye
13x13cm white mercerised cotton 0.0435q/1 polymer
After washing, the cloths were rinsed and tumble dried.
Their reflectances were measured on a ICS Texicon
Spectraflash 500, and the results are given in Table 1 below
as delta E values, calculated from the reflectance values.
The delta E values shown in the table are differences between
washed and unwashed cotton. A high value of delta E
corresponds to more dye transfer than a low value.
Table 1
Example Dye Tranater Ratio
of
L71.9
: E07
inhibition
agent polymer 100:0 90:10 75:25 60:10 0:100
None 41.63 41.63 42.51 41.72 38.77
pVp 41.26 40.06 37.41 26.6 23.82
r PVP/AA (95:51 40.89
pVI 36.55 32.87 25.36 21.55 17.08
q PVI/AA(94:6) 36.03 32.23 26.75 23.68 17.25
pVI/p,p, 37.76 37.03 29.52 25.77 24.41
(83:17)
In addition to the above it was found that a simple ~esr.
using soiled fabrics predicts negative interactions between
the formulation, dye transfer polymer and soil, but it does
not predict positive benefits. It can therefore be used as a
gross negative test to distinguish polymers which can give a
negative in machine tests (worse than the control in the
model test), from those Which will either have no effect, or
. f.. ... _. .,.,....~.................. T ....
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have benefits in the machine tests (equal to or better than
the control) at the higher anionic ratios.
White cotton monitors were washed together with a piece of
dyed test cloth and a piece of soiled test cloth for 30 mins
at 40°C in a solution containing lg/1 active (80:20 LAS/NI),
STP and NaC03 made with Prenton water (26.4°FH). Polymer was
added at 0.0218g/1. The delta E values were calculated from
the reflectance values of the white monitors and the results
compared to the control (no polymer present).
Table 2
Example Dye Traaater Delta 8
Inhibition Polymer
g None 10.19
g pVP 13.18
G PVP/PVI 12.42
PVI 14.04
PVP/AA (95:5) 13.27
6 PVI/AA (94.:6) 9.45
The results for PVP, PVI and PVP/PVI are significantly worse
than the control, and this correlates with the relatively
poor Performance of PVP and PVP/PVI in the washing machine.
In accordance with the invention the inclusion of anionic
monomers in the co-polymer of PVI has significantly reduced
its tendency to interact with soil, whilst not affecting its
ability to bind dyes in solution.
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Redeposition performance
The redeposition performance of the polymers of the invention
was investigated by evaluating their ability to prevent the
transfer of iron oxide forth prestained fabric on to clean
cotton monitor cloths. (0.5 mls of a 1% dispersion of iron
(III) oxide was pipetted onto each monitor cloth and allowed
to dry overnight).
Experiments were conducted in a tergotometer at 60rpm, 4oC,
lOmin using demineralised water.
The reflectance of the monitor cloths was measured as in
Example 1 and delta E values calculated.
The formulation was:
lg/1 nonionic surfactant (E07)
0.87g/L STP
0.522g/L sodium carbonate
0.1305g/L g co-polymer (absent for the control)
Table 3
Example Dye Tanefer Delta E
Inhibition Polymer
None 5.06
PVI 3.79
7 PVI/AA (83:17) 2.84
g PVI/AA(94:6) 3.19
There is thus a clear benefit for pvI/~ polymers.
Example 5 - Dye solubilisation
Without wishing to be bound by theory, it is desirable for
the polymers of the invention to have lower solubilising
capacities compared to the homopolymers of the dye scavenging
monomers. Orange OT, a sparingly water soluble dye from
Aldrich, was purified by recrystalising twice from a
.. _. .. __.. . _. .__...~..~_-.____.. _ . _ r..~~......N _ .
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water/ethanol mixture. This purified dye was then dissolved in
acetone (lOmg/ml).
30u1 (=0.3mg dye) of this solution was added to a vial
containing water. The other components were then added: 0.25g/1
active (a combination of LAS and non-ionic), 0.522g/1 Na2C03)
0.87g/1 STP and 0.1088g/1 polymer (absent for the control). The
total solution was lOmls made with demin water. The vials
containing the solutions were then shaken for 24 hours at 30°C.
They were then centrifuged at 13,000 rpm for 10 mins to
separate out the undissolved dye. The absorbance of the
solutions was measured on a Perkin-Blmer Lambda 16
spectrophotometer at 492nm. In the table below Dye solubilised
refers to the increase in absorbance of solutions (492nm) due
to additional dye solubilised compared to the control without
polymer.
Table 4
gxam~le Dye Traneter Dye Solubiliaed
Inhibition
Polymer 50/50 LAS/E07
pVI 0.031
9 PVI/AA (99:6) 0.021
PVI/AA (83:17) 0.003
The results clearly show that the incorporation of anionic
groups in the polymer has depressed the ability of the
polymer-surfactant complexes to solubilise the water
insoluble dye.
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Examples 11 and 12
A liquid detergent composition was prepared having the
following composition.
Table 5
Wt. $
Ingredient Example 11 Example 12
Alkyl Sulphate - 10
Linear Alkyl Benzene 10 -
Sulphonate
Alkyl ethoxy sulphate
Fatty alcohol ethoxylate 7E0 6 6
Sodium Citrate 2H,0 4 4
Propylene glycol
Sorbitol 4.5 4.5
Na tetra-borate 5H20 3 3
Enzyme to 2$ to 2$
Soil release polymer to 2$ to 2$
PVI/AA 94:6 0.1 to 1 0.1 to 1
water/minors to 100 to 100
i r _.. _.... ~_... T ._ ._~..._~.. ... _ . .
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Example 13
Table 6
The following powdered compositions were prepared.
NaLAS 7.1
NI 7E0 4.7
NI 3E0 3.5
Soap 0.3
Fatty Acid 0.3
STPP 27.1
SCMC 0.2
Na silicate 7.1
CP5 polymer 1.2
Sulphate 16.5
Soil release polymer 0.4
PVI/AA polymer 0.1-1
EAG 1.28
Carbonate 12.00
Bicarbonate 6.00
0.18
Protease
Lipase/Amylase 0.30
Clay 0 to 10$
Cationic surfactant 0 to 2$
Perfume 0.17
Salts/water to 100 '
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Table 7
Na PAS 11.5
NI 7E0 6.3
Soap
2.0
Zeolite A24 24.1
SCMC 0.6
Na Citrate 10.6
Carbonate 23.0
Soil release polymer 0.8
EpG 3.7
PVI/AA 94.6 copolymer 0.1 to 1
Fluorescer
EDTMP 0.4
Percarbonate
CP5 type polymer 0.9
Protease
Lipase 0.1
Perfume 0.4
water/salts to 100
The formulations of Tables 5,6 and 7 had excellent
cleaning and detergency performances with outstanding
colour: care performance on coloured fabrics and mixed
loads of coloured and white fabrics.
_ _ ___~.. _ . T_
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Example (14)~ Anti redeposition results for a copolymer of
MeVI/VP/AA.
The anti-redeposition properties of co-polymers comprising
50/50 MeVI/PVP dye-binding monomers and between 1 and 10% AA
was tested following the method used above under the heading
"Redeposition Performance". The tests were repeated to check
the accuracy (Rep 1 and Rep 2). This time carbon black, not an
iron compound, was used. Tests A, B and C below refer to the
formulation in which the anti-redeposition properties of the
polymer was tested.
The control was the formulation in the absence of polymer. The
MeVI/PVP/AA polymers were prepared following the method of
Example 1. The method of EP-100-890 may also be used to
produce the polymers.
Tergotometer, 40°C, 10 mins, 60 rpm.
Liquor: cloth 25:1 (270 mls:l0.8g)
Demin water
4 13x13 cm white mercerised cotton pieces
1 g/1 synperonic A7 (Syn A7)
0.87 g/1 zeolite A24 (MAP)
1.5 mls 1% dispersion of carbon black in 1 g/1 synperonic A7
The water and carbon black dispersion were placed in the tergo
pot and agitated. The active and zeolite were then added
followed by the cloth. They were washed for 10 mins and then
rinsed twice in demin. They were then spun and tumble dried
and their reflectance values measured as above.
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A) 1 g~Syn A7, 0.522 g/1 NazC03, 0.87 s/1 zeolite
5.56 mls/1, 1°s carbon black suspension, 25:1 liquor: cloth
Polymer Delta E value of white monitor
Rep Rep 2
1
Control 1.4 1.26
MeVI/VP 50:50 1.32 1.14
MeVI/VP/AA 50:50:3 1.14 0.84
MeVI/VP 50:50:5 1.34 0.95
MeVI/VP/AA 50:50:7 0.98 0.71
MeVI/VP/AA 50:50:10 1.08 0.59
B) 1 g/1 Syn A7, 0.522 g/1 Na2C03) no builder
Polymer Delta E value of white monitor
Rep 1 Rep 2
Control 6.81 5.09
MeVI/VP 50:50 2.42 2.08
MeVI/VP/AA 50:50:1 2.47 2.07
MeVI/VP/AA 50:50:3 0.96 1.25
C) 1 Q/1 Syn A7, 0.522 q/1 NaZC03) no builder
Polymer Delta E value of white monitor
Rep 1
Control 7.54
MeVI/VP 50:50 5.65
MeVI/VP/AA 50:50:1 5.96
MeVI/VP/AA 50:50:3 0.36
Tests A, B and C all show the benefits for anti-redeposition
achieved by the MeVI/VP/AA co-polymers. In particular the 3%
and 7% AA exhibit excellent results. The anti-redeposition
effect is achieved over a range of wash concentrations and both
in the presence and absence of builder.
~..__~ _.____.~.__ ~ i
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(ii) Rede~,osition Screen
The 50/50 MeVI/VP/AA co-polymers abpve were also tested as
below.
Shakerbath, 40°C 30 mins, 100 rpm.
100 mls wash solution prepared with Prenton water (26.4°F).
150 mls HDPE bottles.
1 6x6cm Direct Red 80 test cloth.
2 1Ox10cm WFK10D test cloths.
1 13x13 cm white mercerised cotton.
1 g/1 80:20 LAS:NI tPetrelab 550:Synperonic A7)
0.522 g/1 Na2C03
0.87 g/1 STP
0.0218 g/1 polymer (=0.5% on formulation)
The cloths, water, active and then polymer were placed in the
poly bottle and then shaken for 30 mins. When the wash was
complete the cloths were rinsed twice, spun dried and then
tumbled. The reflectance values were measured on an ICS
texicon Spectraflash 500 using the flash 500 programme. These
were converted to Delta E values using the 40ptspec programme.
Each wash was carried out in triplicate to minimise any
experimental variation.
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Polymer E values of white monitors
Rep 1 Rep 2 Rep 3 Average
Control 14.81 12.66 10.23 12.57
MeVI/VP 15.74 14.88 15.18 15.27
50:50
MeVI/VP/AA 14.21 11.98 15.22 13.80
50:50:3
MeVI/VP/AA 10.96 12.96 13.63 12.52
50:50:5
MeVI/VP/AA 13.06 10.71 13.83 12.53
50:50:7
MeVI/VP/AA 8.94 13.99 12.83 11.92
50:50:10
The above table shows the good results for the anti-
redeposition properties of the co-polymers.
Example 15~ MeVI/VP with AA in the presence of anionic and
nonionic surfactants dye transfer performance.
MeVI/VP/AA polymers of varying MeVI/VP ratios and AA
concentrations were tested in a surfactant active system of
varying anionic/nonionic ratios (LAS: N1 ratio).
Conditions: Shakerbath) 40°C, 30 mins, 100 rpm.
100 mls solution made with 26.4°F water in 150 HI7PE
bottle.
1 g/1 total active (combination of LAS and nonionic)
0.52 g/1 NaC03
0.87 g/1 STP
uM Direct Red 80 dye
0.0435 g/1 polymer
13x13cm piece white mercerised cotton sheeting.
I T
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The dye transfer performance was tested as detailed above under
the heading "Dye Transfer Performance".
Polymer Delta
E values
of white
monitors
LAS:NI ratio
100:0 90:10 75:25 60:40 0:100
Control 39.8 41.18 40.11 40 39.44
MeVI/VP/AA 39.6 38.8 32.5 22.6 9.4
50:50:1
MeVI/VP/AA 38.9 37.52 30.75 21.88 15.73
50:50:3
MeVI/VP/AA 38.28 38.13 32.35 25.43 22.91
33:66:3
MeVI/VP/AA 38.32 36.23 32.22 29.05 29.73
25:75:3
The MeVI/VP/AA polymers containing 3% AA were found to give
higher 0E values and hence better performance across the range
of anionic: nonionic (NI) ratios. In the predominantly nonionic
surfactant systems particularly good results were obtained.
ExamQle 16~ MeVI/VP with nonionic monomers.
The dye transfer performance when PEG nonionic monomers were
used was tested as for Example 15.
Polymer Delta
E values
of white
monitors
LAS:NI ratio
100:0 90:10 75:25 60:40 0:100
Control 40.54 40.33 41.10 40.06 38.4
MeVI/VP/PEG (MW 40.35 38.13 34.77 25.67 7.85
300)50:50:5
MeVI/VP/PEG (MW 39.73 38.14 34.10 24.60 9.76
6000) 50:50:5
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The two examples showed good results for dye transfer
performance especially in the presence of larger ratios of
nonionic surfactant ratios.
Example 17~ VI copolymers with other anionic monomers.
The dye transfer performance of co-polymers of VI with either
octanioic acid or hexanoic acid monomers was tested using the
method of Example 15 and following the method detailed under
the heading "Dye Transfer Performance". The control contained
no co-polymer.
Polymer Delta values white monitors
E of
LAS:NI
ratio
100:0 90:10 75:25 60:40 0:100
Control 41.31 41.84 41.39 41.37 40.92
PVI/Octanoic 32.06 29.43 22.34 15.52 8.67
(94.4:5.6)
PVI/Hexanoic 34.61 28.89 23.23 16.09 9.12
(92:8)
Again the copolymers showed good dye-transfer inhibition
performance especially in the presence of predominantly
nonionic surfactant.
.._._.~._ ... __. ~
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Example 18~ MeVI/VP with AA (50:50 with 3% AA) in a fabric
softening composition.
The following fabric softening composition was prepared.
w/w
1 2 3
Di-hardened tallow 5.7 6
dimethyl ammonium
chloride
Varisoft 460 18
di(hardened 13.5
tallowoyloxy)ethyl
dimethyl ammonium
chloride
Fatty acid 2
Perfume 0.3 0.7 1.0
Co-polymer 0.25 0.5 0.75
water added balance balance balance
Example 19~ Granular Main Wash Detergent Compositions
Comprising the Copolymer
Hand Wash Top Loading Front Loading
%w/w %w/w %w/w
NaLas 28 22 7
NI 0 2 3
Soap 0 2 4
STP 24 32 30
Carbonate 15 15 15
Zeolite 0 0 0
Sulphate 15.8 5.8 21.2
Silicate 8 8 8
Enzyme 0.6 1.0 0.6
Fluorescer 0.2 0.2 0.2
S CMC 1 1 1
Co-polymer 0.5 0.75 0.25
The VP/MeVI/AA (50:50 with 3% AA) was included in various
washing compositions as above.
