Note: Descriptions are shown in the official language in which they were submitted.
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LAUNDRY DETERGENT WITH PRETREATMENT ADDITIVE AND ITS USE
This invention relates to granular laundry detergent
compositions containing pre-treatment additives for
intensive treatment of fabric during washing and to a
process for use of the composition during hand washing of
laundry.
BACKGROUND
It is known to include visually contrasting particles in
granular laundry detergent compositions. The particles may
deliver a functional ingredient and/or provide a visual cue.
In US 4082682, a minor proportion of contrastingly colored
elongated soap particles is added to a detergent powder.
The particles comprise a non substantive dye and fluorescer.
The powder comprises a detergency builder compound. The
soap particles contribute detergency to the composition and
reduce foaming. Because the soap particles could sink onto
the fabric it is a stated advantage of the particles that
they do not cause staining of the fabric with which they
come into contact.
In order to improve the visibility and weight effectiveness
of a visual cue it is proposed in GB2358403A to form the
contrasting particle from a film, for example, a coloured
water-soluble polymer film. Such particles are of
significantly larger average particle size in at least one
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dimension than the average particle size of the powder
particles. The examples disclose 5 mm diameter circular or
star shaped colored polymer film particles dry mixed into a
built detergent powder comprising sodium linear alkylbenzene
sulphonate anionic surfactant.
In W02006/079416, it is disclosed that the polymer film
particles used in GB2358403A may be unsuitable for use in
some detergent powder applications, due to poor solubility.
W02006/079416 proposes a film based visual cue of high
solubility. It is suggested to be possible to include
functional ingredients within the film e.g. surface active
agents, perfume, antioxidant, antifoam. The visual cues are
preferably formed of gum Arabic and have a triangular or
"spiky" appearance.
US4176079 describes a detergent powder composition
comprising a water soluble polymer film. An enzyme is
incorporated into a film, which is then cut into squares,
rectangles or strips and added to detergent powder. Typical
film compositions are polyvinyl alcohol 48.7% and nonionic
surfactant 43.8% (balance water and enzyme). The cut
functional film pieces have a surface area of approx 300 mm2
per side. No dye or other additive is added to the film to
make it stand out from the detergent powder. The film may
be plasticised and aerated.
Particularly for laundry hand wash compositions there are
several problems.
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One problem is the pre-treatment of fabrics. Often stains
are difficult to remove during a standard wash and the
consumer needs to pre-treat stains by application of a
composition to the localised area of the stain. This either
requires purchasing several products, which is expensive and
a hassle for the consumer, or the consumer uses more powder,
which is wasteful.
Another problem is to make a cue that adds functionality, so
that its weight effectiveness is improved, especially when
added to water.
Another problem is the effectiveness of visual cues in
reinforcing and conveying perfume attributes to the user.
Another problem is to make a visual cue that persists long
enough to give the desired indication to the user and yet
dissolves well enough not to be a concern to the user,
especially at low temperatures and under hand wash
conditions.
DEFINITIONS
Visual Cue
Means a consumer perceivable point of differentiation in a
detergent composition. This could be a feature of the bulk
composition: e.g. colour, viscosity, size of granules, or it
could be achieved by having visually distinct particles
included in the composition, in a minor amount.
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Visual Cue Particle
Means a coloured speckle, film particle or other solid
visually contrasting particle added to a detergent
composition in a minor amount to function as a visual cue.
Lamellar Visual Cue (or Lamellae)
Means visual cue particles in the form of planar film
material made into shapes. The shapes may be cut from a
sheet of film or may be cast directly. Such lamellae are
also called "film particles".
Flower Shaped (or Flower-Like)
Means planar film shapes (or lamellae) that have the outline
of the shape of a flower with petals. Especially a
stereotypical flower having a central generally circular
area with a number, preferably six, of rotationally
symmetrically dispersed "petals" radiating therefrom.
SUMMARY OF THE INVENTION
According to the present invention there is provided a
granular laundry detergent composition comprising surfactant
and 0.1 to 10 wt% soluble coloured lamellar visual cues made
from a soluble film, wherein the visual cues have a cross-
sectional area of from 5mm2 to 100mm2, characterised in that
the film comprises 10 to 90 wt% surfactant to enable pre-
treatment of fabric and that the film has a relative density
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of 0.2 to 0.8 which ensures that the visual cues float on
water. Advantageously the cross-sectional area of the
visual cues enables them to be scooped into a human hand.
The inclusion of surfactant in the visual cue provides
cleaning functionality. The low relative density and colour
further provides a functional visual cue, which is clearly
visible during the early stages of a hand wash due to its
size and colour, and the fact that it floats. These
attributes, allow the consumer to pick up at least one
visual cue from the surface of the washing solution and rub
it onto a fabric stain to pre-treat the stained area. With
standard speckles, this is physically impossible as they are
too small and they sink. Thus, according to a second aspect
of the invention there is provided a method of using the
composition comprising adding it to water and scooping at
least one visual cue off the surface of the water and then
rubbing it over an area of fabric that requires pre-
treatment, for example a stained area.
DETAILED DESCRIPTION OF THE INVENTION
The detergent formulation
The visual cues may be added to a major proportion of
visually contrasting granular laundry detergent composition.
The precise content of the granular laundry detergent
composition is not critical for putting the invention into
practice. The only restriction is that the granular
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composition must not unduly affect the ability of the visual
cues to separate out to form a separate highly visible
floating portion, when the detergent composition is added to
water.
The granular laundry detergent composition may be built or
unbuilt, low or high foaming, and contain any suitable type
of detersive surfactant. However, it is preferred for
handwash applications that they are built high foaming
compositions comprising anionic surfactant. Phosphate
and/or carbonate builders are preferred. It is especially
beneficial if the surfactant system in the powder has
synergistic compatibility with the anionic surfactant in the
visual cue. Such surfactant combinations are well known in
the field.
The granular composition may be manufactured by any of the
known processes, such as spray drying, dry mixing and
combinations thereof. It may be formed by using adjunct
granules. It is desirable that the visual cues are post
dosed to the composition, preferably using a low shear mixer
to ensure an even distribution of the visual cues through
the granular composition. The film particles are included
in the total composition at a weight percentage in the range
0.01 to 10 wt%, preferably 0.03 to 2 wt% most preferably 0.1
to 1 wt%.
The compositions may suitably contain from 10 to 80%,
preferably from 15 to 70% by weight, of detergency builder.
Preferably, the quantity of builder is in the range of from
15 to 50% by weight.
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Often granular detergents used for hand washing of laundry
include inorganic phosphates, more especially sodium
tripolyphosphate. Other possible phosphate builders are
sodium orthophosphate and pyrophosphate.
Sodium tripolyphosphate is preferably present in an amount
of from 10 to 40 wt%, more preferably from 15 to 35 wt%,
most preferably from 20 to 30 wt%.
Alternative inorganic builders that may be used in place of
or in addition to phosphates are sodium carbonate, layered
silicates, amorphous aluminosilicates.
Alternatively or additionally, the detergent compositions of
the invention may contain as builder a crystalline alkali
metal (preferably sodium) aluminosilicate (zeolite).
Preferred zeolites are zeolite A (zeolite 4A), and zeolite
MAP as described and claimed in EP 384 070B.
Organic builders that may be used include polycarboxylate
polymers such as polyacrylates and acrylic/maleic
copolymers; polyaspartates; monomeric polycarboxylates such
as citrates, gluconates, oxydisuccinates, glycerol mono-,
di- and trisuccinates, carboxymethyloxysuccinates,
carboxymethyloxymalonates, dipicolinates, hydroxyethyl
iminodiacetates, alkyl and alkenyl malonates and succinates;
and sulphonated fatty acid salts.
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
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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.
Other ingredients that are beneficially contained within a
granular detergent composition include any that are
conventionally employed in such compositions. Especially
preferred are ingredients conventionally used in hand
washing compositions. Thus, sodium sulphate, enzymes,
fluorescers, dye transfer inhibiters, anti redeposition
agents, shading dye and enzymes are desirably included.
Although it is possible to include bleach, this is less
preferred for hand wash compositions.
Use of a green granule in the composition is advantageous if
used with film colours that are associated with flowers.
The visual cue effect due to this floral colour selection is
further amplified by the green "stem" colour contrast in the
granular composition. This is especially important for use
with perfumes evocative of nature, such as floral perfumes.
The Film particle
a) Composition of the visual cues
The visual cues are made of coloured film. The essential
components of the film are polymer, surfactant and a non-
fabric-substantive colorant. Optional further ingredients
are: adjuncts to assist in the manufacture of the film, for
instance release agents, other functional ingredients, and
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water. Besides its effect of control of relative humidity
of the film, water also assists in plasticising the film and
regulates its solubility.
The polymer may be selected from water soluble film forming
polymers, especially those used in formulation of detergent
powders. Preferred polymers include polymers which dissolve
and/disperse completely in water within 30 minutes with
agitation at a temperature anywhere in the range of from 20
to 60 C.
Preferred water soluble polymers are those capable of being
cast into a film or solid mass, for example as described in
Davidson and Sittig, Water-Soluble Resins, Van Nostrand
Reinhold Company, New York (1968). Preferred water-soluble
resins include polyvinyl alcohol, cellulose ethers,
polyethylene oxide, starch, polyvinylpyrrolidone,
polyacrylamide, polyvinyl methyl ether-maleic anhydride,
polymaleic anhydride, styrene maleic anhydride,
hydroxyethylcellulose, hydroxypropylmethylcellulose,
polyethylene glycols, carboxymethylcellulose, polyacrylic
acid salts, alginates, acrylamide copolymers, guar gum,
casein, ethylene-maleic anhydride resin series,
polyethyleneimine, ethyl hydroxyethylcellulose, ethyl
methylcellulose, hydroxyethyl methylcellulose, sugars. Lower
molecular weight water-soluble, polyvinyl alcohol film-
forming resins are preferred.
Polyvinyl alcohols preferred for use therein have an average
molecular weight anywhere between 1,000 and 1,000,000,
preferably between 5,000 and 250,000, for example between
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15,000 and 150,000. Hydrolysis, or alcoholysis, is defined
as the percent completion of the reaction where acetate
groups on the resin are substituted with hydroxyl, -OH,
groups, A hydrolysis range of from 60-99% of polyvinyl
alcohol film-forming resin is preferred, while a more
preferred range of hydrolysis is from about 70-90% for
water-soluble, polyvinyl alcohol film-forming resins. The
most preferred range of hydrolysis is 80-89%. As used in
this application, the term "polyvinyl alcohol" includes
polyvinyl acetate compounds with levels of hydroloysis
disclosed herein.
Another suitable polymer is a polyvinyl alcohol film, made
of a polyvinyl alcohol copolymer having a comonomer having a
carboxylate function.
The preferred grade of PVA picks up water only at an RH well
above that of granular detergent compositions. Thereby, it
protects the other film ingredients from decomposition by
water and soluble dyes from bleeding. Fluorescer can be
included in the film to increase the effect of the visual
cue. A low level of suitably coloured dye may also be
included to counter any yellowing. Shading dye and Aloe
Vera may be included in the film too.
The visual cue film particle may comprise 10 to 80% polymer
or polymer mixture.
The cue must contain surfactant to remove stubborn stains.
In particular, the visual cue needs to have a minimum of 10
% surfactant, but preferably > 20 %. Although any suitable
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surfactant or surfactant system, may be used. The
surfactant is preferably an anionic surfactant, especially
if the granular composition comprises a builder. At least
wt% anionic surfactant is preferably included in the
5 film.
Suitable anionic surfactants include are well-known to those
skilled in the art. Examples of high-foaming sulphonate or
sulphate type surfactants include alkylbenzene sulphonates,
10 particularly linear alkylbenzene sulphonates having an alkyl
chain length of C8-C15; primary and secondary alkylsulphates,
particularly C8-C15 primary alkyl sulphates; olefin
sulphonates; alkyl xylene sulphonates; dialkyl
sulphosuccinates; and fatty acid ester sulphonates. Sodium
salts are generally preferred.
Further information is given in the open literature, for
example, in "Surface-Active Agents and Detergents", Volumes
I and II, by Schwartz, Perry and Berch.
The preferred anionic surfactants are alkylbenzene
sulphonates, more especially linear alkylbenzene sulphonate
(LAS), which is preferably present in an amount of from 12
to 24 wt%, more preferably from 12 to 22 wt% and especially
from 15 to 22 wt%.
Even more preferred are primary alcohol sulphates (PAS),
particularly C8-C18r preferably C12-CI5, primary alcohol
sulphates. A particularly preferred surfactant is primary
alcohol sulphate (PAS) with a carbon chain length of 12.
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Visual cue Film particles containing up to 50 % PAS, may be
used.
The film may additionally include a second surfactant. The
second surfactant is preferably chosen from amphoteric
surfactants, zwitterionic surfactants, nonionic surfactants
and ethoxylated anionic surfactants.
Preferred amphoteric second surfactants are amine oxides.
The most preferred amine oxide is coco dimethylamine oxide.
Preferred zwitterionic second surfactants are betaines, and
especially amidobetaines, for example, coco amidopropyl
betaine.
Preferred nonionic second surfactants include the primary
and secondary alcohol ethoxylates, especially the C8-C20
aliphatic alcohols ethoxylated with an average of from 1 to
moles of ethylene oxide per mole of alcohol, and more
20 especially the C10-C15 primary and secondary aliphatic
alcohols ethoxylated with an average of from 1 to 10 moles
of ethylene oxide per mole of alcohol.
Preferred ethoxylated anionic second surfactants, include
alkyl ether sulphates (ethoxylated alcohol sulphates).
Also suitable for use as second surfactants in the visual
cues of the present invention are C8-C18 alkyl
monoethanolamides, for example, coco monoethanolamide.
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The second surfactant system used in the film particle may
additionally comprise minor amounts, e.g. less than 5% of
the film, of cationic surfactant.
The surfactant, or surfactant system, fulfils two functions
in the film. It enhances the solubility of the film and it
provides detersive action to enable the film to be used
directly on wetted stains. Surfactant may be included at a
level of up to 90 wt%, preferably up to 75 wt%, most
preferably up to 60 wt% in the film.
The visual cue needs to be easily visible in wash liquor as
well as against the background of the detergent formulation,
therefore it needs to be coloured. Non fabric-substantive
colorants are included in the film composition at a level of
0.05 to 0.5 wt%, preferably 0.1 to 0.3 wt%, most preferably
0.15 to 0.25 wt%.
Suitable colorants include any that are used to colour
detergent liquids or powders. Yellow, blue, violet, lilac,
purple, red, orange, green, pink are preferred colours.
White may also be used if the remainder of the detergent
composition is of sufficient contrast. However, white is
not preferred because it does not have very high visibility
on the water surface.
Preferably, the film is the same colour as detergent variant
The "colour" of the variant is the predominant colour of the
packaging and marketing material used to represent that
variant. However, it is also within the scope of the
invention to have different coloured visual cue film
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particles for different types of pre-treatment, all included
in one composition in one pack. Once added to water one
colour or a mix of coloured cues may easily be selected and
scooped up for use either separately, or in combination.
Yellow cues did not have a high visual contrast from a white
powder before film cues. Now, with the improved contrast
due to the higher cross section area, they can be used as
natural floral cues along with the preferred floral colours.
b) Size and shape of the visual cue film particles
To achieve the required level of visibility to function as a
visual cue in the composition and to be easily seen when
floating on the water surface the film particles need to be
significantly bigger than the average detergent powder
particles. The particle size of granules in the detergent
composition typically ranges from 0.1 to 2 mm. The film
particles are also advantageously a different shape from the
generally spherical granules in the detergent composition.
The film particle size in two dimensions is preferably at
least 3 mm, more preferably at least 4 mm. In the third
dimension the film particle is the thickness of the film,
which is at most lmm, preferably 0.4 mm, more preferably
0.25mm, most preferably 0.2 mm thick.
Being this flat shape also assists the film particles to
float.
Each visual cue film particle has a cross sectional area of
between 5 mm2 and 100 mm2. Preferably, the number of
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particles that will be dosed to each wash lies in the range
20 to 200. The preferred cross-sectional area of a film
particle is 10 to 30 mm2, preferably 15 to 20 mm2, whereby
the size of the film particle enables it to be scooped
easily into a human hand from the wash liquor. It is
preferred that if the composition is a built granular
laundry detergent composition then the visual cues should
have a maximum diameter at least twice that of the detergent
granules.
The invention also provides a shaped visual cue, which does
not segregate during mixing, handling, or transport, but
which does segregate in use. Cues may be shaped into the
form of petals, hexagons, squares, circles, stars.
Preferably, the visual cue is petal shaped and the petal is
the same colour as detergent variant.
To maximise the impact of the film particle as a visual cue
for perfume the film is cut into the shape of something
natural and normally associated with a smell, e.g. petal,
flower, floret etc. Ideally the shape and also, most
ideally, the colour of the film particle is linked to the
perfume. We have found that the size is less important to
cue for perfume than either shape or colour.
In a modification of the shape of the film particle it is
formed to resemble a petal with a central dot or hole to
make it look more like a real flower. The latter further
reduces the weight too.
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The film may be used flat or it may be formed into a three
dimensional shape, for example by making larger bubbles from
two sheets of film laminated together around their edges, or
in some other more complex configuration, like "bubble
wrap". Provided buoyancy is maintained, the cavities may be
filled with other ingredients that assist in the pre-
treatment of fabrics. These may be liquids, pastes or
solids. Such ingredients may additionally or alternatively
be included into the film itself.
c) relative density of the film particles
The film used should float on water. To achieve this for
sufficient time while the visual cue dissolves we have found
that it should have a density of between 200 and 800 g/l,
preferably between 230 and 500 g/l, most preferably 250 to
400 g/l. Surprisingly we have found that film particles of
this density and having the preferred particle dimensions
set forth above, do not unduly segregate from a detergent
powder during manufacture or during storage and
transportation. This is advantageous because it means that
the particles provide a uniform level of visibility on the
surface of the pack during use and it also assists in
ensuring that roughly the same number of particles are does
to the wash and thus ensures that the ability to pre-treat
with the floating particles is not hindered by their
separation in the pack.
The low relative density ensures that the film particles
float on the surface of an aqueous wash liquor. This is
achieved by a combination of the chemicals used and the
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degree of aeration applied to the film during its
manufacture. The bubbles of air also diffuse light, which
has the effect of enhancing visibility and distinctiveness
of the film, especially when it is floating on the water
surface. The bubbles are also thought to improve the
dissolution of the film.
The film may be made of low density by inclusion of porosity
in the manufacturing stage. This can be by means of large
light diffusing bubbles of gas beaten in to the mixture
during film making or it can be achieved by gas evolved from
film ingredients (e.g. citric acid and carbonate). The
bubbles can be nano-bubbles. Film with capillaries may also
be used. Also films with ribs that form open capillaries
and meshes or films with active and lightweight ingredients
in its "pores".
Method of use of the detergent composition with pre-treater
The composition is added to water. This can be done before
or after the clothes. Immediately, the pre-treatment film
particles float and appear to separate from the remainder of
the composition. The consumer is reassured to see that the
brightly coloured particles are not coming into direct
contact with the clothes (although no harm would be done if
they did). The film particles slowly dissolve on the
surface over a period of 5 minutes to 30 minutes. The
powder or liquid dissolves in the water faster and delivers
builder to the water; if it is a built composition.
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If pre-treatment is needed, the consumer may scoop film
particles off the water surface using their hand and use
these particles to pretreat fabric. Between 3 and 10
particles may easily be scooped up at once, depending on the
level of treatment desired. Thus, the consumer is in
control of the dosage of surfactant to be used for pre-
treatment.
Furthermore, use of the cue in this way, in conjunction with
a wash liquor, to provide building or some other enhancement
of the detergency of the cue gives improved detergency
relative to use of the cues on their own.
A further advantage of the visual cue floating is that it
avoids the problems of variable speed of dispersion and/or
dissolution that can occur if the particle gets embedded in
clothing at the bottom of the wash liquor. This is a
particular problem for hand washing processes.
A yet further advantage of the visual cue floating during
the early stages of the wash is that the film particles are
highly visible to the consumer. This means that they
effectively continue to communicate the benefit of improved
fragrance or other benefit for which they are designed to
cue. For instance, by selecting cues in the shape and
colour of small florets it has been shown that the consumer
perceives a floral perfume more hedonistically and expresses
clear preference for a formulation containing the perfume
and the cues over one without cues or with a cue that does
not look so much like a floret (i.e. a hexagonal cue of
equivalent area). For communicating perfume or fabric care
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benefits during the wash cues that float are also preferred
by potential consumers over cues that sink.
Examples
Under static conditions shapes need to dissolve not faster
than 10 minutes and not slower than 30 minutes, preferably
between 15 and 25 minutes.
Pre-treatment
A white carbonate built granular laundry detergent
formulation comprising a floral perfume and primary alcohol
sulphate as the main surfactant was combined with 0.5 wt%
yellow film cues comprising 47wt% polyvinylalcohol, 48wt%
primary alcohol sulphate, non substantive yellow colorant
and water. The relative density of the film was approx 0.3.
The yellow film was just under 0.2 mm thick on average and
had been cut into floret shapes with a maximum diameter of
approximately 5 mm in the other two dimensions.
A standard dosage of the composition including the visual
cues was added to water at 35 C and immediately the visual
cue florets floated and dispersed over the surface of the
water in the washing vessel and contributed to a perception
of a pleasant floral perfume given off by the wash liquor.
A handful of florets were easily scooped up using the
fingers as a sort of strainer and the wet florets were
rubbed with finger ends over a piece of cotton cloth stained
with tomato oil. The stain was easily removed in a few
seconds. As a control experiment, at the same time an
identical stain was wetted with the wash liquor and rubbed
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by a finger end and the stain was still visible for some
time longer than the pre-treatment with the visual cue
florets containing anionic surfactant.
