Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
12-10-2001 EP00113T,
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FABRIC CARE COMPOSITION
The present invention relates to a fabric care composition comprising a
s novel colour care and stain treatment system. The present invention also
relates to a method of treating fabric using the novel colour care and stain
treatment system. The present invention further relates to the use of the
novel colour care and stain treatment system in fabric care treatment.
io
Background of the Invention
The present invention is concerned with fabric treatment that takes place
after use of the fabric, in particular to reverse degradation of fabric that
is occurs as a result~of that use, for example soiling and staining. Such
treatments are referred to herein as fabric care. Fabric care treatments
include laundering and the application of non-detergent-based fabric care
products, such as spray-on products. Considerable attention has been
focused on components for inclusion in fabric care compositions which are
2o specifically intended for colour care. For example, these components may
comprise dye transfer inhibitors, stain removers, photofading inhibitors,
and fluorescence inhibitors.
European patent application EP 0 786 517 discloses a fabric wash
2s detergent composition in which a specific polymer system is included to
provide stain removal benefits. International patent application no.
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PCT/EP 97107289 discloses fabric treatment compositions comprising a
sunscreen material for preventing sun damage to colour. WO 95/13354
discloses compositions comprising polymers such as PVPNO and N-vinyl
pyrollidonelN-vinyl imidazoIe copolymers as dye transfer inhibitors. EP-
s A-0035470 discloses a textile treatment composition which comprises a
photobleaching component. The photobleach material has some effect
against stains, but can also attack dye.
FR 2579990 discloses 'singlet oxygen' photo-bleaches for use in 'colour
to safe' detergent compositions As is well known 'singlet' refers to the spin
multiplicity of the electrons and not to their pairing. WO 96!03481
discloses a sunscreen/anti-oxidant mixture. As can be appreciated,
sunscreens are preferably designed to be light stable and not to initiate
radicals as this would defeat their objective.
Fabric care compositions comprising radical photoinitiator systems that
operate by a hydrogen abstraction mechanism or a bond cleavage
mechanism are. described in our co-pending patent application no
WO 01!07549. If the photoinitiator has a high log P value (where P is the
octanol-water partion coefficient) ie, it is relatively hydrophobic, then
little dye damage is likely to result when the compositions are applied to
coloured fabric but, in other cases, dye damage may result.
The present invention aims to provide further colour care and stain
2s treatment compositions which contain radical initiators. The invention
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also aims to reduce the likelihood of damage to the dye in a coloured
fabric when the compositions are used for the treatment of such a fabric.
Radical photoinitiators themselves are well-known and used in the
unrelated fields of polymerisation, polymer cross-linking and curing
reactions in materials. Radical terminators are also known in these, and
other unrelated, technical fields.
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Definition of the Invention
The present invention accordingly provides a fabric care composition,
comprising at least one radical initiator and at least one radical terminator.
s
The present invention further provides a fabric care treatment method,
comprising treating the fabric with at least one radical initiator in the
presence of at least one radical terminator.
1o The present invention further provides the use of a composition
comprising at least one radical initiator and at least one radical terminator
in a fabric care treatment method.
It has been found that the radical photoinitiators of the present invention
Is will act on stains without the need for agitation. This has the advantage
that they can be used in simple application methods. Further, damage to
fabrics such as fibrillation can be avoided.
The radical initiator systems according to the present invention are found
2o to be soluble or dispersible in other media than water and can be used on
dry-clean only garments.
The compositions of the invention have the surprising advantage that they
reduce dye damage in coloured fabrics relative to corresponding
2s compositions containing no radical terminator, whilst retaining effective
stain bleaching properties. It was unexpected that the radical initiator and
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the radical terminator did not simply cancel each other out when used
together in the composition to give substantially no stain bleaching
properries.
s
Detailed Description of the Invention
Radical Initiators:
to Preferably the radical initiators are radical photoinitiators. Chemical and
thermal radical initiators are less preferred.
It has been found that the radical photoinitiators of the present invention
have the advantage that they are stable in solution if kept in the substantial
~s absence of light. It is found that they do not degrade spontaneously on
storage.
Preferably the radical initiators are selected from hydrogen abstraction
radical photoinitiators, bond-cleavage radical photoinitiators and mixtures
2o thereof.
Radical photoinitiators preferred for use in the present invention are
components which produce radicals capable of attacking stains on fabric,
on photoexcitation by one of the following routes:
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Hydrogen Abstraction
Hydrogen abstraction radical photoinitiators operate according to the
following reaction:
s
light kl
X X*+R- X~+R~
where X is the radical photoinitiator and R-H is a hydrogen donating
to compound.
Suitable examples of hydrogen abstraction radical photoinitiators X
include benzophenones, acetophenones, pyrazines, quinones and benzils.
is Suitable examples of hydrogen donating compounds R-H include organic
molecules containing an aliphatic C-H group and include propan-2-ol, and
compounds comprising a cellulose, polyester, or nylon backbone, for
example.
2o kl is the rate constant of the hydrogen abstraction reaction. Preferably,
the rate constant kl is greater than 104 mol-1 ls-1 when RH is propan-2-ol.
Bond Cleavage Radical Photoinitiators
2s Bond cleavage radical photoinitiators operate according to the following
reaction:
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light k2
Y Y* R~~+ RZ~
k2 is the rate constant of the bond-cleavage reaction. Preferably, k2 is
greater than 10~ s-1.
Suitable bond cleavage radical initiators may be selected from the
following groups:
to
(a) alpha amino ketones, particularly those containing a benzoyl moiety,
otherwise called alpha-amino acetophenones, for example 2-methyl
1-[4-phenyl]-2-morpholinopropan-1-one (Irgacure 907, trade mark),
(2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)-butan-1-one
(Irgacure 369, trade mark);
(b) alphahydroxy ketones, particularly alpha-hydroxy acetophenones, eg
( 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-
one) (Irgacure 2959, trade mark), 1-hydroxy-cyclohexyl-phenyl-
2o ketone (Irgacure 184, trade mark);
(c) phosphorus-containing photoinitiators, including monoacyl and
bisacyl phosphine oxide and sulphides, for example 2-4-6-
(trimethylbenzoyl)diphenyl-phosphine oxide, bis(2,4,6-
2s trimethylbenzoyl)-phenyl-phosphine oxide (Irgacure 819, trade
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mark), (2,4,6-trimethylbenzoyl)phenyl phosphinic acid ethyl ester
(Lucerin TPO-L (trade mark) ex BASF);
(d) dialkoxy acetophenones;
s
(e) alpha-haloacetophenones; and
(f) trisacyl phosphine oxides.
to (g) benzoin and benzoin based photoinitiators
Suitable radical photoinitiators are disclosed in
WO 9607662 (trisacyl phosphine oxides), US 5399782 (phosphine
sulphides), US 5410060, EP-A-57474, EP-A-73413 (phosphine oxides),
~s EP-A-088050, EP-A-0117233, EP-A-0138754, EP-A-0446175 and US
4559371.
Suitable photoinitiators are disclosed for example in EP-A-0003002 in the
name of Ciba Geigy, EP-A-0446175 in the name of Ciba Geigy, GB
20 2259704 in the name of Ciba Geigy (alkyl bisacyl phosphine oxides), US
4792632 (bisacyl phosphine oxides), US 5554663 in the name of Ciba
Geigy (alpha amino acetophenones), US 5767169 (alkoxy phenyl
substituted bisacyl phosphine oxides) and US 4719297 (acylphosphine
compounds) .
2s
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Radical photoinitiators are discussed in general in A.F. Cunningham, V.
Desorby, K. Dietliker, R. Husler and D.G. Leppard, Chemia 48 (1994)
423-426. They are discussed in H. F. Gruber Prog. Polym. Sci. 17(1992)
953-1044. _ _
s
without wishing to be bound by theory, it is preferred that the radical
photoinitiators all react through their excited triplet state, to reduce the
influence of the cage effect.
io The radical photoinitiator suitably undergoes one of the reactions set out
above when excited by radiation falling generally in the .range 290-800
nm. For example, natural sunlight, which comprises light in this region,
will be suitable for causing the radical photoinitiator to undergo one of the
reactions described above. Preferably, the radical photoinitiator has a
is maximum extinction coefficient in the ultraviolet range (290-460 nm)
which is greater than 100 mol''lcm 1. Suitably, the radical .photoinitiator is
a solid or a liquid at room temperature. Preferably, the treated fabric is
exposed to light until the stain is removed or all photoinitiator has reacted.
It will be appreciated that the time taken for stain removal and/or
2o substantially complete reaction of the photoinitiator will depend on the
intensity of the light. In typical terrestrial light conditions, the time of
exposure may, for example, range from a few seconds to a few days, .
preferably 1 second to 6 hours.
2s The method of the invention preferably comprises a step of exposing the
treated fabric to light, more preferably sunlight, even more preferably
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direct sunlight. When the method is carried out as part of a laundering
process, the exposure to light conveniently involves drying the fabric in
sunlight. However, the treated fabric can be exposed to light in other
ways, such as, for example, using a source of artificial light.
Suitably, the radical photoinitiator is substantially colourless and gives
non-coloured photo products upon undergoing one of the reactions set out
above.
io Optionally, the compositions comprise sensitisers such as thioxanthones,
for example as described in EP-A-0088050, EP-A-0138754.
Preferred Radical Photoinitiator Systems
Is The present inventors have discovered that radical photoinitiators having a
specified hydrophobicity, measured by their log P value, have a
particularly preferred effect. All materials for the removal of stains also
have a tendency to attack dye. The preferred radical photoinitiator
systems have a particularly beneficial balance of stain removal versus dye
2o attack tendency.
Preferably, the radical photoinitiators have a high log P value, where log
P is the octanol-water partition coefficient. It is preferred that the radical
photoinitiators have a log P measured at 25°C in excess of 2.5 and more
2s preferably in excess of 4Ø
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Radical Terminators
The radical terminators which are used in the compositions and methods
of the invention react rapidly with reactive free radicals to give non-
s reactive products. "Reactive free radicals" are the free radicals which are
formed from the radical initiator or by the reaction of these free radicals
with molecules which are present in the environment in the region of the
stain.
1o The reaction of the radical terminators (T) with reactive free radicals (R)
to give non-reactive products can be summarised by the following
equation:
k3
Is R ~ + T ~ non-reactive products
The non-reactive products can, for example, be relatively stable (and
relatively unreactive) radicals or non-radical molecules or ions.
2o The rate constant k3 for the above reaction is preferably greater than 104
M-1 s-1, more preferably greater than 10~ M-1 s-1 or even more preferably
at or near to the diffusion controlled limit (ie, close to 8RT/3E, where T is
the temperature, R is the gas constant and E is the viscosity).
2s Suitable radical terminators include, for example, stable (ie, non-
reactive)
radicals eg, compounds containing nitroxide (N-O~) radicals, radicals
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derived from hindered semiquinones or radicals derived from hindered
phenols. These radicals act as radical terminators by reaction with the
reactive free radicals to form a non-radical molecule or ion.
s Suitable radical terminators also include, for example, compounds which
react with reactive free radicals to form the stable radicals mentioned in
the preceding paragraph. Thus, hindered amines (HALS; hindered amine
light stabilisers) which are capable of forming nitroxide radicals, hindered
phenols and hindered hydroquinones can also act as effective terminators.
to
Preferred radical terminators for use in the invention include ascorbic acid
(vitamin C) and chromanols such as vitamin E.
The chemistry of radical terminators is well-known and is described in,
is for example, Pospisil et al, "Oxidation Inhibition in Organic Materials",
Volumes I and II, CRC Press, 1990. Rate constants k3 for the reactions
of radical terminators with reactive free radicals are given in, for
example, Landolt-Bornstein, "Radical Reaction Rates in Liquids", Fisher
H, Hellwege K-H, (Springer-Verlag) 1963-1997.
The radical terminators which may be used in the compositions and
methods of the invention can be single radical terminator compounds or
mixtures containing two or more different radical terminators.
It is surprising that, in the present invention, when radical terminators are
used in conjunction with radical initiators, the two do not merely cancel
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each other out but, instead, still give effective stain bleaching whilst
reducing damage to the dye in a coloured fabric. This benefit is
particularly, although not exclusively, observed when the radical
terminator is water soluble and the use of water soluble radical terminators
s is therefore preferred.
The ratio of the amounts (by weight) of radical terminator to radical
initiator used in the compositions and methods of the invention can be, for
example, from 100:1 to 1:100, preferably 10:1 to 1:10, more preferably
l0 5:1 to 1:5.
Fabric Care Compositions
The present invention is suitable for use in industrial or domestic fabric
Is wash compositions, fabric conditioning compositions and compositions for
both washing and conditioning fabrics (so-called through the wash
conditioner compositions). The present invention can also be applied to
industrial or domestic non-detergent based fabric care compositions, for
example spray-on compositions.
Fabric Wash Compositions
Fabric wash compositions according to the present invention may be in
any suitable form, for example powdered, tableted powders, liquid or
2s solid detergent bars.
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Fabric wash compositions according to the present invention comprise a
fabric wash detergent material selected from non-soap anionic surfactant,
nonionic surfactants, soap, amphoteric surfactants, zwitterionic surfactants
and mixtures thereof.
s
Suitable anionic surfactants are well known to the person skilled in the art
and include alkyl benzene sulphonate, primary and secondary alkyl
sulphates, particularly Cs-Cps primary alkyl sulphates; alkyl ether
sulphates; olefin sulphonates; alkyl xylene sulphonates, dialkyl
to sulphosuccinates; ether carboxylates; isethionates; sarcosinates; fatty
acid
ester sulphonates and mixtures thereof. The sodium salts are generally
preferred.
Nonionic surfactants are also well known to the person skilled in the art
is and include primary and secondary alcohol ethoxylates, especially Cs-CZo
aliphatic alcohol ethoxylated with an average of from 1 to 20 moles of
ethylene oxide per mole of alcohol, and more especially the Coo-Cps
primary and secondary aliphatic alcohols ethoxylated with an average of
from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-
2o ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol
monoethers and polyhydroxy amides (glucamide). Mixtures of nonionic
surfactant may be used.
Detergent compositions suitable for use in domestic or industrial automatic
2s fabric washing machines generally contain anionic non-soap surfactant or
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nonionic surfactant, or combinations of the two in suitable ratio, as will be
known to the person skilled in the art, optionally together with soap.
Many suitable detergent-active compounds are available and fully
s described in the literature, for example in "Surface-Active Agents and
Detergents", Volumes I and II, by Schwartz, Perry & Berch.
Anionic surfactant is suitably present at a level of from 5 wt % to 50 wt % ,
preferably 10 wt%-40 wt% based on the fabric treatment composition.
Nonionic surfactant is suitably present at a level of 1-20 wt% , preferably
io 5-15 wt% .
The total amount of surfactant present will depend upon 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 fabric,
is an amount of from 5 to 40 wt% is generally appropriate.
Detergency Builder
The detergent compositions of the invention will generally also contain
20 one or more detergency builders. The total amount of detergency builder
in the compositions will suitably range from 5 to 80 wt % , preferably from
lOto60wt%.
Inorganic builders that may be present include sodium carbonate, if
2s desired in combination with a crystallisation seed for calcium carbonate,
as disclosed in GB 1 437 950 (Unilever ); crystalline and amorphous
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aluminosilicates, for example, zeolites 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 514B (Hoechst). Inorganic phosphate builders, for example,
s 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
to 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 Na20. A12O3. 0.8-6 5102
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
2o sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula above).
Both the amorphous and the crystalline materials can be prepared readily
be reaction between sodium silicate and sodium aluminate, as amply
described in the literature.
2s Suitable crystalline sodium aluminosilicate ion-exchange detergency
builders are described, for example, in GB 1 429 143 (Procter &
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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 commercially available zeolite 4A now widely used
s in laundry detergent powders. The zeolite builder incorporated in the
compositions of the invention may be maximum aluminium zeolite P
(zeolite MAP) 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
Io 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 MAP having a silicon to aluminium ratio
not exceeding 1.07, more preferably about 1.00. The calcium binding
is capacity of zeolite MAP is 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, and acrylic
2o phosphinates; monomeric polycarboxylates such as citrates, gluconates,
oxydisuccinates, glycerol mono-, di- and trisuccinates,
carboyxmethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
hydroyxethyliminodiacetates, alkyl- and alkenylmalonates and succinates,;
and sulphonated fatty acid salts. This list is not intended to be
2s exhaustive.
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Especially preferred organic builders are citrates, suitable 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
to
Detergent compositions according to the invention may also suitably
contain a peroxy bleach system for example, inorganic persalts or organic
peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
Is 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.
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).
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The compositions may further comprise a photobleach system as
described, for example, in EP-A-0035470.
Fabric Softening Composition
The fabric treatment composition of the present invention may be a fabric
conditioning composition or it may comprise fabric conditioner.
Fabric Softening Compound
to
The fabric softening compound is preferably a cationic nonionic or
anionic fabric softening compound.
The fabric softening compound may be a quaternary ammonium
Is material comprising a polar head group and one or two alkyl or alkenyl
chains. The fabric softening compound may also be a nonionic fabric
softening compound such as a fabric softening oil, a fabric softening
silicone composition or a fabric softening ester composition such as
sugar esters.
Particularly preferably, the fabric softening compound has two long
chain alkyl or alkenyl chains with an average chain length greater than
C~4, more preferably each chain has an average chain length greater
than C~4, more preferably at least 50 % of each long chain alkyl or
2s alkenyl group has a chain length of Cps.
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It is preferred if the long chain alkyl or alkenyl groups of the fabric
softening compound are predominantly linear.
It is highly preferred if the fabric softening compounds are substantially
s water-insoluble. Substantially insoluble fabric softening compounds in
the context of this invention are defined as fabric softening compounds
having a solubility less than 1 x 10-3 wt % in demineralised water at
20°C, preferably the fabric softening compounds have a solubility less
than 1 x 10-4, most preferably the fabric softening compounds have a
Io solubility at 20°C in demineralised water from 1 x 10-3 to 1 x
10-6.
Well-known species of substantially water-insoluble quaternary
ammonium compounds having the formula:
R1
R4 N~ R2 X-
R3
Is wherein R1 and RZ represent hydrocarbyl groups having from 12 to 24
carbon atoms; R3 and R4 represent hydrocarbyl groups containing 1 to 4
carbon atoms; and X is an anion, preferably selected from halide,
methyl sulphate and ethyl sulphate groups are preferred.
2o Representative examples of these quaternary softeners include di(tallow
alkyl) dimethyl ammonium methyl sulphate; dihexadecyl dimethyl
ammonium chloride; di(hydrogenated tallow alkyl) dimethyl ammonium
chloride; dioctadecyl dimethyl ammonium chloride; di(hydrogenated
tallow alkyl) dimethyl ammonium methyl sulphate; dihexadecyl diethyl
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ammonium chloride; di(coconut alkyl) dimethyl ammonium chloride,
ditallow alkyl dimethyl ammonium chloride and di(hydrogenated tallow
alkyl) dimethyl ammonium chloride (Arquad 2HT Trade Mark) .
s Other preferred softeners contain esters or amide links, for example
those available under the trade names Accosoft 580, Varisoft 222, and
Stepantex.
Particularly preferred fabric softening compounds are water-insoluble
to quaternary ammonium materials which comprise a compound having
two C~z-~s alkyl or alkenyl groups connected to the molecule via at least
one ester link. It is more preferred if the quaternary ammonium
material has two ester links present. The preferred ester-linked
quaternary ammonium material for use in the invention can be
is represented by the formula:
R1
2o R1 N+ (CHz)a-T-RZ X-
(CHz)n-T-RZ
2s wherein each Rl group is independently selected from C~-a alkyl,
hydroxyalkyl or Cz-4 alkenyl groups; and wherein each R2 group is
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independently selected from Cs-as alkyl or alkenyl groups; T is -C(O)-
O- or -O-C(O)-; X- is any suitable anion and n is an integer from 0-5.
Particularly preferred is diethyl ester) dimethyl ammonium chloride
(DEEDMAC).
s
A second preferred type of quaternary ammonium material can be
represented by the formula:
OOCR2
to
(R~)3N + - (CH2)n -- CH X-
CHZOOCRZ
is wherein R~, n, X- and Rz are as defined above.
It is advantageous for environmental reasons if the quaternary ammonium
material is biologically degradable.
2o Preferred materials of this class such as 1,2 bis[hardened tallowoyloxy]-3-
trimethylammonium propane chloride and their methods 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-
2s hydroxy trimethylammonium propane chloride.
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The fabric softening agent may also be a polyol ester quat (PEQ) as
described in EP 0 638 639 (Akzo).
Other Ingredients
s
The compositions of the invention can also contain one or more optional
ingredients, selected from pH buffering agents, perfume carriers,
fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition
agents, enzymes, optical brightening agents, opacifiers, anti-shrinking
to agents, anti-wrinkle agents, anti-spotting agents, germicides, fungicides,
anti-corrosion agents, drape imparting agents, antistatic agents and ironing
aids.
The present invention may be in the form of a dilute or concentrated
is aqueous solution or suspension, for example as described in WO
97/15651, WO 95/27769. Alternatively, the fabric softening composition
may be in the form of a powder for use in the rinse cycle of an automatic
washing machine. Alternatively, the fabric softening composition may be
in the form of a sheet comprising fabric conditioning compositions for use
2o in a tumble dryer, for example as disclosed in WO 95/27777.
Alternatively, the fabric conditioning composition may be in the form of a
substantially non-aqueous concentrate as described in international patent
application no. PCT/EP99/00497.
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Fabric wash detergent compositions according to the present invention
may further include through the wash softening material, such as cationic
fabric softener.
Non-Detergent-Based Fabric Care Products
The present invention can also be used in non-detergent-based fabric care
products. For example, the product may comprise the stain removal
system as the principal ingredient. For example, non-detergent based
to compositions may comprise solutions of the stain removal system of the
present invention in a suitable solvent, such as isopropanol, alcohol etc.
The compositions may comprise aerosol or spray-on compositions. They
may be in the form of sticks, bars, dab-on compositions, for example
absorbed into sponges for application to the surface etc.
The present invention will be further described by way of example only
with reference to the following examples.
Examples
All quantities are in percent or parts by weight unless indicated otherwise.
The following radical initiators are used in the present examples. They
are available commercially as initiators for free radical polymerisation
under the trade marks set out below from Ciba Specialty Chemicals.
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Irgacure 184 - an a-hydroxyacetophenone photoinitiator.
Irgacure 819 - bis(2,4,6-trimethyl benzoyl) - phenyl phosphine oxide (log
P = 5.8, measured at 25°C).
s
The radical terminator used was 4-hydroxy-2,2,6,6-tetramethyl-1-
piperidinyloxy free radical (TEMPOL ex Aldrich)
to Example 1
Curry, chilli, bolognese and ~-carotene stained cotton cloth was purchased
from Equest (aged 3 days and packed under nitrogen). The amounts of
Irgacure 184 and TEMPOL listed in the table, were dissolved in ethanol
is and applied to the stained cloth. The cloth was dried, and then irradiated
in a Weatherometer (WOM), with the WOM operated at the outside
Florida sunlight setting, for 12 minutes. In separate experiments the
stained cloth was wetted before placing in the WOM. The results are
listed in Tables 1 and 2 below. Addition of TEMPOL did not reduce the
2o efficiency of bleaching (bleaching was above that of light alone, which
gave an average reduction of approximately 9 OE units dry and 12 OE
units wet) and TEMPOL on its own did not provide significant extra
bleaching. Stain bleaching was measured on a reflectometer and
expressed in CIELAB OE values.
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The bleaching and protection were also observed when the stained cloth
was exposed to ambient light in the UK.
184 TEMPOL stain OE before OE after
treatment treatment
0.1 0 ~3-carotene 50.3 7.6
0.1 0 bolognese 9.8 8.5
0.1 0 chilli 31. 8 25.7
0.1 0 curry 47.1 31.7
0.1 0 average value34.9 18.4
0.1 0.1 a-carotene 52.5 9.3
0.1 0.1 bolognese 10.7 9.0
0.1 0.1 chilli 31.2 24.9
0.1 0.1 curry 46.3 30.2
0.1 0.1 average value35.2 18.4
Table 1, values for dry cloth. OE calculated compared to white original
cloth.
,12-10-2001 EP001137
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A mended 9 October 2001 - 26 -
184 TEMPOL stain OE before OE after
- treatment treatment
0.1 0 ~3-carotene s0.5 3.s
0.1 0 bolognese ~ 10.7 7.1
0.1 0 chilli 33.0 23.2
0.1 0 curry 48.3 26.2
0.1 0 average value 3s.6 14.3
. 0.1 0.1 ~-carotene s2.s 4.9
0.1 0.1 bolognese 10.7 ' 7.1
0.1 0.1 chilli ' 31.2 19.1
0.1 0.1 curry 46 .3 2s . 9
0.1 0.1 average value 3s.2 14.3
Table 2 Values for wet cloth
The padding procedure above was then repeated using cloth dyed with the
s dyes listed in Table 4 (cloths obtained from Veebee Tech, Harrogate,
LJK). Dye damage was measured on a reflectometer and expressed in
CIELAB DE values compared to the original. The results are shown in
Table 3, and show that dye damage is significantly reduced in the presence
of TEMPOL. Thus the combination of radical initiator and TEMPOL
io provides a better cleaning to care effect.
AMENDED SHEET
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184 TEMPOL dye bleaching-wet dye bleaching-dry
0.1 0 4.3 2.1
0.1 0.1 1.0 1.3
Table 3 effect of TEMPOL on dye damage.
no. name type g/kg
Procion
1 Red HE-7B hydrazone 0.5
2 Scarlet HE-3G hydrazone and azo 0.5
3 Crimson HE-XL hydrazone 0.5
4 Yellow HE-6G azo 1.0
Red HE-GXL hydrazone 0.5
6 Blue HE-XL anthraquinone and hydrazone2.0
7 Turquoise H-A phthalocyanine 5.0
8 Navy HE-XL hydrazone 1.0
Remazol
9 Red RB hydrazone 1.0
Golden Yellow RNL azo 1.0
11 Brill Red RBS hydrazone 2.0
12 Yellow FG azo 1.0
13 Orange FR hydrazone 2.0
14 Navy GG hydrazone 2.0
Turquoise G phthalocyanine 2.0
16 Black B hydrazone 1.0
Table 4 Dye set used.
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Example 2
The experimental procedure of Example 1 was repeated using Irgacure
819. The results are summarised in Table 5, stain reduction and dye
damage are quoted in OE values. Again, there is little effect on bleaching
but the dye damage is greatly reduced, ie, a better clean/care regime. The
initial average staining was 40 4E units, and irradiation was performed
wet.
819 TEMPOL average stain average dye
reduction* bleaching
0.1 0 18.5 3.5
0.1 0.1 14.9 0.5
to
Table 5
*values are quoted above a control irradiated without initiator.
Example 3
The experiments were repeated using Irgacure 184 and, instead of
TEMPOL, Vitamin C (ascorbic acid, Sigma). Again, dye damage was
reduced but stain bleaching was not. (In this case Irgacure 184 was
applied from ethanol, dried then Vitamin C was applied from water).
2o Thus, 0.1 % 184 and 0.1 % Vitamin C gave an average stain reduction of
19.6 and dye damage of 1.1 when irradiated wet for 12 minutes.
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Example 4
The experiments were repeated using Vitamin E(Sigma) and Irgacure 184.
Again dye damage was reduced, however in this case there was some
s decrease in stain bleaching. Vitamin E is not water soluble.
Example 5
The following rinse conditioner formulation was prepared:
HEQ 1 - 4
Perfume - 0. 3
is Ascorbic acid - 0.66
Irgacure 819 (trade mark) - 0. 66
Water - to 100
1 HEQ = 1,2 bis [hardened tallowoyloxy]-3-trimethylammonium
propanechloride, ex Hoechst.
3 grams of this rinse conditioner were dissolved in 600 grams of cold
2s water. 18 grams of cotton sheeting were placed in it for 5 minutes. At
the end of this time, the cotton was removed and dried. The reflectance
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spectrum of the cotton sheeting was studied at 320 nm using a Spectraflash
SF60 (trade mark) reflectometer.
It was calculated from the reflectance results that approximately 0.003
s of radical photoinitiator (based on the weight of the cloth) had been
delivered.
Example 6
to An oily tomato stain was created by smearing an oily tomato paste (ex
Sacla; ingredients:-rehydrated sun dried tomatoes, sunflower seed oil,
white wine vinegar, salt, sugar, flavourings, garlic, black pepper and
lactic acid) on white cotton. Once the paste was applied, it was left for 30
minutes then washed in detergent without bleach or fluorescer (Persil
Is Colour (trade mark) powder) at 20°C then rinsed. (All water was
demineralised). The wash did not remove all the stain.
Ethanol solutions containing 0.0019 mol 1-1 Irgacure 819 (trade mark)
and:-
20 (a) nothing else
(b) 0.0035 mol 1-1 TEMPOL
(c) 0.0037 mol 1-1 10-DOXYL nonadecane (Sigma) were padded onto
the stains and onto the dyed cotton (according to the procedure
outlined in Example 1); the cloths were dried then wet with water
2s then irradiated in a WOM for 6 minutes. The results are
summarised in the table below.
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treatment stain reduction, average dye damage,
DE DE
(a) 19.2 3.5
(b) 19.3 0.5
(c) 17.8 2.5
although the less water soluble 10-DOXYL nonadecane does reduce dye
s damage it is not as effective as TEMPOL.
Example 7
A base washing powder was produced containing:-
to
chemical amount
Linear sodium alkyl-benzene sulphonate 23. 60
(LAS)
sodium tripolyphosphate 19.22
sodium silicate 4.81
sodium sulphate 28.59
calcite 10. 30
minors 1. 08
water 12.49
Powders were also created as above further containing 9.5 % Irgacure 819
(trade mark) and 9.5 % Irgacure 819 (trade mark) with 10 % TEMPOL.
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The three powders were dissolved in water and used to wash cotton dirtied
by an oily tomato stain (as per Example 5) and cotton dyed with cibacron
red and cibacron turquoise at 0.1 % owf. After washing, the clothes were
irradiated wet in a WOM for 6 minutes. Both Irgacure 819 (trade mark)
s containing formulations gave better cleaning than the control. The
formulation containing TEMPOL gave less dye damage.
