POLYMER TREATMENT METHOD
Field of the Invention
[0001] The present invention relates to the aqueous cleaning of soiled substrates,
specifically textile fibres and fabrics, using a cleaning system comprising re-useable
polymeric particles. More specifically, the invention is concerned with a system wherein
said polymeric particles themselves are intermittently cleaned, in order to extend their
useable lifetime.
Background to the Invention
[0002] Aqueous cleaning processes are a mainstay of both domestic and industrial
textile fabric washing. On the assumption that the desired level of cleaning is achieved,
the efficacy of such processes is usually characterised by their levels of consumption of
energy, water and detergent. In general, the lower the requirements with regard to these
three components, the more efficient the washing process is deemed. The downstream
effect of reduced water and detergent consumption is also significant, as this minimises
the need for disposal of aqueous effluent, which is both extremely costly and detrimental to
the environment.
[0003] Such washing processes, whether in domestic washing machines or their
industrial equivalents (usually referred to as washer extractors), involve aqueous
submersion of fabrics followed by soil removal, aqueous soil suspension, and water
rinsing. In general, the higher the level of energy (or temperature), water and detergent
which is used, the better the cleaning. The key issue, however, concerns water
consumption, as this sets the energy requirements (in order to heat the wash water), and
the detergent dosage (to achieve the desired detergent concentration). In addition, the
water usage level defines the mechanical action of the process on the fabric, which is
another important performance parameter; this is the agitation of the cloth surface during
washing, which plays a key role in releasing embedded soil. In aqueous processes, such
mechanical action is provided by the water usage level, in combination with the drum
design, for any particular washing machine. In general terms, it is found that the higher the
water level in the drum, the better the mechanical action. Hence, there is a dichotomy
created by the desire to improve overall process efficiency (i.e. the reduction of energy,
water and detergent consumption), and the need for efficient mechanical action in the
wash. For domestic washing in particular there are defined wash performance standards
specifically designed to discourage the use of such higher levels in practice, in addition to
the obvious cost penalties which are associated with such usage.
[0004] Current efficient domestic washing machines have made significant strides
towards minimising their consumptions of energy, water and detergent. EU Directive
92/75/CEE sets a standard which defines washing machine energy consumption in
kWh/cycle (cotton setting at 60 °C), such that an efficient domestic washing machine will
typically consume <0. 19 kWh/kg of washload in order to obtain an 'A' rating . If water
consumption is also considered, then 'A' rated machines use <9.7 litres/kg of washload.
[0005] Detergent dosage is then driven by manufacturer recommendations but, again, in
the domestic market, for a concentrated liquid formulation , a quantity of 35 ml (or 37 g) for
a 4-6 kg washload in soft and medium hardness water, increasing to 52 ml (or 55 g) for a
6-8 kg washload (or in hard water or for very dirty items) is typical (see, for example,
Unilever pack dosage instructions for Persil® Small & Mighty). Hence, for a 4-6 kg
washload in soft/medium water hardness, this equates to a detergent dosage of 7.4-9.2
g/kg whilst, for a 6-8 kg washload (or in hard water or for very dirty items), the range is 6.9-
9.2 g/kg .
[0006] Energy, water and detergent consumptions in the industrial washing process
(washer-extractors) are considerably different, however, and usages of all three resources
are less constrained, since these are the principal factors in reducing cycle time - which is,
of course, more of a consideration than in the case of domestic use. For a typical
industrial washer extractor (25 kg washload rated and above), energy consumption is 0.30-
1.0 kWh/kg, water is at 20-30 litres/kg, and detergent is much more heavily dosed than for
domestic washing . The exact level of detergent used will depend on the amount of soiling ,
but a range of 20- 100 g/kg is representative.
[0007] Thus, it can be taken from the above discussion that it is the performance levels
in the domestic sector which set the highest standard for an efficient fabric washing
process, and that these are: an energy consumption of <0. 19 kWh/kg, a water usage of
<9.7 litres/kg, and a detergent dosage of approximately 8.0 g/kg. However, as previously
observed, it is becoming increasingly difficult to reduce the water (and, hence, energy and
detergent) levels in a purely aqueous process, due to the minimum requirement to wet the
fabric thoroughly, the need to provide sufficient excess water to suspend the soil removed
in an aqueous liquor and, finally, the necessity to rinse the fabric.
[0008] Heating of the wash water is then the principal use of energy, and a minimum
level of detergent becomes necessary in order for an effective concentration to be reached
at the operating wash temperature. Means to improve mechanical action without
increasing the water level used would, therefore, make any aqueous wash process
significantly more efficient (i.e. yield further reductions in energy, water and detergent
consumption). It should be noted that mechanical action itself has a direct effect on the
detergent level, since the greater the level of soil removal which is achieved through
physical force, the less that is required of the detergent chemistry. However, increasing
the mechanical action in a purely aqueous washing process has certain associated
drawbacks. Fabric creasing readily occurs in such processes, and this acts to concentrate
the stresses from mechanical action at each crease, resulting in localised fabric damage.
Prevention of such fabric damage (i.e. fabric care) is of primary concern to the domestic
consumer and the industrial user.
[0009] In the light of these challenges which are associated with aqueous washing
processes, the present inventors have previously devised a new approach to the problem,
which allows the deficiencies demonstrated by the methods of the prior art to be
overcome. The method which is provided eliminates the requirement for the use of large
volumes of water, but is still capable of providing an efficient means of cleaning and stain
removal, whilst also yielding economic and environmental benefits.
[0010] Thus, in WO-A-2007/1 28962, there is disclosed a method and formulation for
cleaning a soiled substrate, the method comprising the treatment of the moistened
substrate with a formulation comprising a multiplicity of polymeric particles, wherein the
formulation is free of organic solvents. Preferably, the substrate is wetted so as to achieve
a substrate to water ratio of between 1:0.1 to 1:5 w/w, and optionally, the formulation
additionally comprises at least one cleaning material, which typically comprises a
surfactant, which most preferably has detergent properties. In preferred embodiments, the
substrate comprises a textile fibre and the polymeric particles comprise, for example,
particles of polyamides, polyesters, polyalkenes, polyurethanes or their copolymers but,
most preferably, are in the form of nylon beads.
[0011] The use of this polymeric cleaning method, however, presents a requirement for
the cleaning particles to be efficiently separated from the cleaned substrate at the
conclusion of the cleaning operation, and this issue is addressed in WO-A-201 0/094959,
which provides a novel design of cleaning apparatus requiring the use of two internal
drums capable of independent rotation, and which finds application in both industrial and
domestic cleaning processes.
[0012] In co-pending WO-A-201 1/064581 , there is provided a further apparatus which
facilitates efficient separation of polymeric cleaning particles from the cleaned substrate at
the conclusion of the cleaning operation, and which comprises a perforated drum and a
removable outer drum skin which is adapted to prevent the ingress or egress of fluids and
solid particulate matter from the interior of the drum, the cleaning method requiring
attachment of the outer skin to the drum during a wash cycle, after which the skin is
removed prior to operating a separation cycle to remove the cleaning particles, following
which the cleaned substrate is removed from the drum.
[0013] In a further development of the apparatus of WO-A-20 11/064581 , there is
disclosed in co-pending WO-A-20 11/09881 5 a process and apparatus which provides for
continuous circulation of the polymeric cleaning particles during the cleaning process, and
thereby dispenses with the requirement for the provision of an outer skin.
[0014] Further benefits in terms of reduced power and consumable requirements for the
cleaning method originally proposed in WO-A-2007/1 28962 have been disclosed in copending
GB Patent Application No. 101831 8.4, where the technology has been refined to
achieve at least equivalent cleaning performance whilst employing significantly reduced
levels of detergents and much lower process temperatures.
[0015] The apparatus and methods disclosed in the foregoing prior art documents have
been highly successful in providing an efficient means of polymeric cleaning and stain
removal which also yields significant economic and environmental benefits. As reported in
WO-A-2007/1 28962, re-use of the polymeric particles is possible but it is possible that
cleaning performance can fall if the same particles are used for more than three wash
cycles. Co-pending application WO-A-201 1/09881 5 states that the particle re-use aspect
of the cleaning processes disclosed therein is preferred, however, and it is obviously
beneficial from both economic and environmental considerations. WO-A-201 1/098815
goes further, therefore, by describing means to extend the useable lifetime of said particles
by subjecting them to a cleaning operation in a second chamber of the washing apparatus.
This can be achieved by sluicing said chamber with clean water in the presence or
absence of a cleaning agent, which may be selected from at least one of surfactants,
enzymes and bleaches. Alternatively, cleaning of the polymeric particles may be
achieved as a separate stage in the rotatably mounted cylindrical cage of the disclosed
apparatus - i.e. by running the washing process without any washload in the machine. It
is also mentioned that, after cleaning, the polymeric particles are recovered such that they
are available for use in subsequent washes.
[0016] Hence, in attempting to further develop the method of the cleaning processes
from WO-A-2007/1 28962 and co-pending WO-A-201 1/09881 5, the present inventors are
now seeking to provide a specific process and formulation for cleaning the polymeric
particles which, in combination, maximise the number of fabric washes that can be
successfully performed by the machine before repeat cleaning of the polymeric particles is
required. In addressing this issue, they have de facto also maximised the useable lifetime
of the polymeric particles, and minimised the economic and environmental burden
generated by the polymeric particle cleaning process.
Statements of Invention
[0017] Thus, according to a first aspect of the present invention, there is provided a
method for the treatment of polymeric particles recovered after use in cleaning processes
for soiled substrates, said method comprising treating said particles with a particle cleaning
agent.
[0018] Typically, the processes for cleaning soiled substrates comprise the treatment of
the moistened substrate with a formulation comprising a multiplicity of said polymeric
particles.
[0019] The substrate cleaned by said cleaning processes may comprise any of a wide
range of substrates, including, for example, plastics materials, leather, paper, cardboard,
metal, glass or wood. In practice, however, said substrate most preferably comprises a
textile fibre or fabric, which may comprise either a natural material, such as cotton, or a
synthetic textile material, for example nylon 6,6 or a polyester.
[0020] Polymeric particles are typically treated according to the method of the invention
following use in said cleaning processes for soiled substrates, and may subsequently be
re-used in further such cleaning processes with little or no reduction in their cleaning
efficiency. Particles may be cleaned and re-used in this manner on multiple occasions,
and optimum performance has been achieved with particles which have been cleaned
according to the method of the invention and re-used for the cleaning of soiled substrates
in up to 500 substrate cleaning cycles.
[0021] Thus, a second aspect of the present invention also envisages a method for
cleaning a soiled substrate, said method comprising the steps of:
(a) treating polymeric particles recovered after use in cleaning processes for
soiled substrates, said treatment comprising treating said particles with a
particle cleaning agent; and
(b) treating a moistened substrate with a formulation comprising a multiplicity of
said treated polymeric particles.
[0022] The treatment process for said polymeric particles involves treating the particles
with a particle cleaning agent which comprises at least one surfactant. Optimally said
particle cleaning agent is an aqueous liquor. Optimally, said particle cleaning agent also
comprises at least one additional component selected from enzymes, oxidising
agents/bleaches and biocides.
[0023] Optionally said particle cleaning agent may additionally comprise one or more
additional components selected from stabilisers, wetting agents and solvents, with the
balance of the formulation being made up with water. Said additional components typically
provide improved chemical stability and dissolution properties.
[0024] Preferred surfactants comprise surfactants having detergent properties, and said
particle cleaning agent preferably comprises a detergent formulation. Said surfactants
may comprise anionic, non-ionic, cationic, ampholytic, zwitterionic and/or semi-polar nonionic
surfactants. Preferred enzymes include, but are not limited to, amylase, protease,
lipase and mannanase. Oxygen or chlorine derived bleaches may be combined with said
surfactants, in addition to suitable liquid biocides to inhibit mould and bacterial growth at
the particle surface.
[0025] Suitable examples of apparatus for the execution of the methods of the invention
are disclosed in WO-A-20 10/094959, WO-A-201 1/064581 and WO-A-201 1/098815. The
claimed method for the cleaning of soiled substrates additionally provides for separation
and recovery of the polymeric particles, which are then re-used in subsequent washes.
[0026] Thus, the polymeric particle cleaning operation can conveniently be carried out in
a second chamber of a washing apparatus as described in WO-A-201 1/09881 5. This can
be achieved by sluicing said chamber with clean water in the presence or absence of said
particle cleaning agent. Preferably, cleaning of the polymeric particles may be achieved as
a separate stage in the rotatably mounted cylindrical cage of this apparatus - i.e. by
running the washing process without any washload in the machine. In this embodiment,
the temperature of the water used to aid circulation of the polymeric particles in the
machine, is generally heated to a temperature from 5 ° to 95 °C, more preferably from 30°
to 75°C, and most preferably from 35° to 65 °C. Said treatment is typically carried out for a
duration of from 5 to 120 minutes, more preferably from 10 to 90 minutes, and most
preferably from 15 to 60 minutes, at the desired temperature. The recited times and
temperatures are also appropriate to other embodiments of the invention.
[0027] Said polymeric particles may comprise any of a wide range of different polymers.
Specifically, there may be mentioned polyalkenes such as polyethylene and
polypropylene, polyesters and polyurethanes. Preferably, however, said polymeric
particles comprise polyester or polyamide particles, most particularly particles of
polyethylene terephthalate, polybutylene terephthalate, nylon 6, and nylon 6,6, most
preferably in the form of beads. Said polyesters and polyamides are found to be
particularly effective for aqueous stain/soil removal, whilst polyalkenes are especially
useful for the removal of oil-based stains. Optionally, copolymers of the above polymeric
materials may be employed for the purposes of the invention.
[0028] Specifically, the properties of the polymeric materials may be tailored to particular
requirements by the inclusion of monomeric units which confer desired properties on the
copolymer. Thus, the polymers may be adapted to attract particular staining materials by
comprising co-monomers which, inter alia, are ionically charged, or include polar moieties
or unsaturated organic groups. Examples of such groups may include, for example, acid
or amino groups, or salts thereof, or pendant alkenyl groups.
[0029] Furthermore, the polymeric particles may comprise either foamed or unfoamed
polymeric materials. Additionally, the polymeric particles may comprise polymers which
are either linear or crosslinked, and said particles may be solid or hollow.
[0030] As previously stated, various polyester and/or polyamide homo- or co-polymers
may be used for the polymeric particles, including polyethylene terephthalate, polybutylene
terephthalate, nylon 6 and nylon 6,6. Preferably, the nylon comprises nylon 6,6
homopolymer having a molecular weight in the region of from 5000 to 30000 Daltons,
preferably from 10000 to 20000 Daltons, most preferably from 15000 to 16000 Daltons.
The polyester will typically have a molecular weight corresponding to an intrinsic viscosity
measurement in the range of from 0.3-1 .5 dl/g as measured by a solution technique such
as ASTM D-4603.
[0031] The polymeric particles are of such a shape and size as to allow for good
flowability and intimate contact with the soiled substrate, which typically comprises a textile
fibre or fabric. A variety of shapes of particles can be used, such as cylindrical, spherical
or cuboid; appropriate cross-sectional shapes can be employed including, for example,
annular ring, dog-bone and circular. In preferred embodiments of the invention, said
particles are in the form of beads and, most preferably, comprise cylindrical or spherical
beads.
[0032] The particles may have smooth or irregular surface structures and can be of solid
or hollow construction. Particles are of such a size as to have an average mass of 1-50
mg, preferably from 10-30 mg, more preferably from 12-25 mg.
[0033] In the case of cylindrical beads, the preferred particle diameter is in the region of
from 1.0 to 6.0 mm, more preferably from 1.5 to 4.0 mm, most preferably from 2.0 to 3.0
mm, and the length of the beads is preferably in the range from 1.0 to 5.0 mm, more
preferably from 1.5 to 3.5 mm, and is most preferably in the region of 2.0 to 3.0 mm.
[0034] Typically, for spherical beads, the preferred diameter of the sphere is in the region
of from 1.0 to 6.0 mm, more preferably from 2.0 to 4.5 mm, most preferably from 2.5 to 3.5
mm.
[0035] Once cleaned according to the method of the invention, the polymeric particles
can be used in substrate washing cycles within apparatus such as that described in WO-A-
201 1/09881 5. Repeat substrate washing cycles can then be carried out with numerous
washloads of soiled substrates, typically soiled textile fibres or fabrics, until either the
cleaning performance, or the colour of the polymeric particles themselves, becomes
unacceptable to the operator. Both factors are dependent on the level of soiling
encountered in the washloads concerned and, hence, it is not possible to precisely specify
an exact number of such washes before a polymeric particle cleaning cycle should be
performed. Experience, however, dictates that for a lightly soiled garment washload (e.g.
household laundry), it will be typically be >20 fabric wash cycles before particle cleaning
becomes necessary whereas, with very heavily soiled industrial laundry washloads (e.g.
car mechanics' overalls), this will typically drop to once in every 6 such wash cycles. In
addition, if there is a switch from a very heavily soiled washload, such as that specified, to
a subsequent washload which is particularly colour sensitive (e.g. white table linen), it will
be necessary to perform a particle cleaning cycle ahead of that switch, in order to ensure
no carry over of soil between the two washes. Hence, it can be seen that polymeric
particle cleaning can be an important contributor to fabric washing processes as carried
out in the apparatus of WO-A-201 1/098815 and co-pending applications, as described
above.
[0036] When carrying out the substrate washing processes, the ratio of polymeric
particles to substrate is generally in the range of from 0.1 : 1 to 10:1 w/w, preferably in the
region of from 0.5:1 to 5:1 w/w, with particularly favourable results being achieved with a
ratio of between 1: 1 and 3:1 w/w, and especially at around 2:1 w/w. Thus, for example, for
the cleaning of 5 g of substrate, typically textile fabric, 10 g of polymeric particles,
optionally coated with surfactant, would be employed in one embodiment of the invention.
The ratio of polymeric particles to substrate is maintained at a substantially constant level
throughout the wash cycle.
[0037] The substrate cleaning method according to the invention may be applied to a
wide variety of substrates, as previously stated. More specifically, it is applicable across
the range of natural and synthetic textile fibres and fabrics, but it finds particular application
in respect of nylon 6,6, polyester and cotton fabrics.
[0038] Prior to treatment according to the method of the invention, the substrate is
moistened by wetting with water, to provide additional lubrication to the cleaning system
and thereby improve the transport properties within the system. Thus, more efficient
transfer of the at least one cleaning material to the substrate is facilitated, and removal of
soiling and stains from the substrate occurs more readily. Most conveniently, the substrate
may be wetted simply by contact with mains or tap water. Preferably, the wetting
treatment is carried out so as to achieve a substrate to water ratio of between 1:0.1 to 1:5
w/w; more preferably, the ratio is between 1:0.2 and 1:2, with particularly favourable
results having been achieved at ratios such as 1:0.2, 1: 1 , 1: 1 .2 and 1:2. However, in some
circumstances, successful results can be achieved with substrate to water ratios of up to
1:50, although such ratios are not preferred in view of the significant amounts of effluent
which are generated.
[0039] As a consequence of employing the substrate cleaning method of the present
invention, excellent cleaning performance may be achieved whilst using significantly
reduced levels of detergents and much lower process temperatures. Thus, fabric and fibre
cleaning operations according to the invention, whilst possible at temperatures of up to
95°C, are typically carried out at temperatures not exceeding 65°C, and optimum
performance is generally achieved at 5-35 °C, generally for a duration of between 5 and 45
minutes, and usually in a substantially sealed system.
[0040] It is throughout the repeated substrate washing cycles, carried out as described
above, that the polymeric particles are treated by the intermittent cleaning process
according to the present invention, in order to extend their useable lifetime.
[0041] According to a further aspect of the present invention, there is provided a
formulation for cleaning a soiled substrate, said formulation comprising a multiplicity of
polymeric particles, wherein said particles have been treated with a particle cleaning agent
according to the method of the first aspect of the invention.
[0042] Said substrate may comprise any of a wide range of substrates, including, for
example, plastics materials, leather, paper, cardboard, metal, glass or wood. In practice,
however, said substrate most preferably comprises a textile fibre or fabric, which may
comprise either a natural material, such as cotton, or a synthetic textile material, for
example nylon 6,6 or a polyester.
[0043] In one embodiment, said formulation may essentially consist only of said
multiplicity of polymeric particles treated with said particle cleaning agent but, optionally, in
other embodiments said formulation further comprises at least one additional fabric
cleaning agent. Preferably, the at least one additional fabric cleaning agent comprises at
least one surfactant. Preferred surfactants comprise surfactants having detergent
properties and said additional fabric cleaning agents preferably comprise detergent
formulations. Said surfactants may comprise anionic, non-ionic, cationic, ampholytic,
zwitterionic, and/or semi-polar non-ionic surfactants. Optionally, said at least one
additional fabric cleaning agent also comprises at least one enzyme and/or bleach.
[0044] Said formulation is preferably used in accordance with the method of the second
aspect of the invention, and is as defined in respect thereof. Additional additives may be
incorporated in said formulation, as appropriate; said additives may include, for example,
anti-redeposition additives, optical brighteners, perfumes, softeners and starch which can
enhance the appearance and other properties of the cleaned substrate.
[0045] The formulation and the methods of the present invention may be used for either
small or large scale processes of both the batchwise and continuous variety and,
therefore, find application in both domestic and industrial cleaning processes. Excellent
performance can also result from the use of fluidised beds, and this is particularly the case
when the method of the second aspect of the invention is used for carrying out wet
cleaning processes.
Brief Description of the Drawings
[0046] Embodiments of the invention are further described hereinafter with reference to
the accompanying drawings, in which:
Figures 1(a) and (b) show an apparatus suitable for use in the performance of the
method of the invention.
Detailed Description of the Invention
[0047] A typical operation of the polymeric particle cleaning cycle according to the
method of the present invention can be carried out in cleaning apparatus such as that
described in WO-A-201 1/098815. Said apparatus is illustrated in Figures 1(a) and (b),
wherein there is shown an apparatus comprising housing means (1) having a first upper
chamber having mounted therein a rotatably mounted cylindrical cage in the form of drum
(2) (perforations not shown) and a second lower chamber comprising sump (3) located
beneath said cylindrical cage. The apparatus additionally comprises, as first recirculation
means, bead and water riser pipe (4) which feeds into separating means comprising a
bead separation vessel (5), including filter material, typically in the form of a wire mesh,
and a bead release gate valve which feeds into feeder means comprising bead delivery
tube (6) mounted in cage entry (7). The first recirculation means is driven by pumping
means comprising bead pump (8). Additional recirculation means comprises return water
pipe (9), which allows water to return from the bead separation vessel (5) to the sump (3)
under the influence of gravity. The apparatus also comprises access means shown as
loading door (10), though which material for cleaning may be loaded into drum (2). The
main motor (20) of the apparatus, responsible for driving the drum (2), is also depicted.
[0048] At the commencement of the polymer particle cleaning cycle the apparatus
contains no washload, and the polymeric particles to be cleaned are held with an amount
of water (usually 1: 1 w/w) in said second chamber (3) of the apparatus. This water is
typically some or all of the residual rinse water used in the previous substrate washing
cycle. The polymeric particles and water are then pumped by the pumping means (8) to
the separating means (5), from which the polymeric particles are transferred to the
rotatably mounted cylindrical cage (2). The water passing through said separating means
(5) is returned to the second chamber (3). Pumping continues until the polymeric particles
are essentially removed from the second chamber (3). At this stage of the process said
cage (2) is held stationary, in order to retain the polymeric particles. The perforations in
the wall of the rotatably mounted cylindrical cage (2) will allow some polymeric particles to
fall back into the second chamber (3), but the number doing so is very small, as the ratio of
the perforation diameter to that of the particle is only slightly greater than 1 (typically 1.2-
3.5), and the action of pumping the polymeric particles into the cage (2) causes these to
quickly accumulate, so as to prevent further flow of particles through said perforations.
Pumping continues until transfer of the polymeric particles into the cage (2) is complete.
[0049] Optionally the polymeric particle cleaning agent can be introduced into said
second chamber (3) and mixed with the water therein at this stage in the procedure.
Alternatively, the particle cleaning agent can be diluted in fresh water and introduced
directly onto the particles in the cage (2), by using spray means through the access means
(10) at the front of the cage (2), in order to facilitate more uniform coverage of the particles.
The particle cleaning agent can also be introduced via the separating means (5), although
this is a less preferred mode of operation.
[0050] The pumping means (8) then acts to circulate the polymeric particles, water and
particle cleaning agent into the now rotating cage (2), such that the fluids and a quantity of
the particles are continually exiting through the perforations in the cage wall. In all such
embodiments of the invention, the process of circulating the particles, water and particle
cleaning agent from the second chamber (3), via pumping means (8) and separating
means (5) to the rotating cage (2) and back to the second chamber (3), then continues
throughout the particle cleaning cycle. Optionally, the water used may be heated, so as to
further improve cleaning performance. In this embodiment of the invention the water
circulated with the polymeric particles in the machine is preferably heated to a temperature
of from 5° to 95°C, more preferably from 30° to 75 °C, and most preferably from 35° to
65°C. Said treatment is carried out for a duration of from 5 to 120 minutes, more
preferably from 10 to 90 minutes, and most preferably from 15 to 60 minutes, at the
desired temperature.
[0051] Following this part of the process, the particles are again pumped into the cage
(2) via the separating means (5), said cage (2) once again being held stationary. The
water returned to the second chamber (3) from the separating means (5) during this
transfer now contains the soil liberated from the particles, and so it is drained away, to be
replaced with fresh water. Optionally the second chamber (3) may be sluiced with fresh
water a number of times, or additionally cleaned with water containing a cleaning agent, in
order to remove any remaining contaminants. The water, with or without cleaning agent,
may optionally be heated. With the second chamber (3) now full of fresh water, the
rotatably mounted cage (2) is once more caused to rotate, and the polymeric particles are
allowed to fall back into the second chamber (3).
[0052] At the conclusion of the polymeric particle cleaning process, the apparatus is then
ready to begin again the process of substrate cleaning, typically textile fibre and fabric
washing, as described above and, for example, in WO-A-201 1/09881 5. The degree of
soiling of the fabric washed will dictate the frequency with which the particle cleaning cycle
is required to be re-run. Obviously, more heavily soiled fabrics will necessitate more
frequent particle cleaning and vice versa. It is therefore not possible to precisely specify
an exact number of fabric washes before a particle cleaning cycle is required to be
performed. Experience, however, dictates that, for a lightly soiled garment washload (e.g.
household laundry), it will be typically be >20 fabric wash cycles before particle cleaning
becomes necessary whereas, with very heavily soiled industrial laundry washloads (e.g.
car mechanics' overalls), this will typically drop to once in every 6 such wash cycles. In
addition, if there is a switch from a very heavily soiled washload, such as that described, to
a subsequent washload which is particularly colour sensitive (e.g. white table linen), it will
be necessary to perform a particle cleaning cycle ahead of that switch, in order to ensure
no carry over of soil between those washes.
[0053] Thus, by careful control of the composition of the particle cleaning agent, and the
temperature and time of the particle cleaning cycle, the number of fabric washes that can
be successfully performed by the machine before repeat cleaning of the polymeric
particles is required can be maximised. In so doing, the useable lifetime of the polymeric
particles is also maximised, and the economic and environmental burden generated by the
polymeric particle cleaning process is minimised.
[0054] In order to achieve the desired benefits associated with the invention, the particle
cleaning agent is optimally specifically formulated to include a combination of surfactants,
enzymes, oxidising agents/bleaches and biocides, together with any necessary stabilisers,
wetting agents and solvents. Preferred surfactants comprise surfactants having detergent
properties, and said particle cleaning agent preferably comprises a detergent formulation.
Said surfactants may comprise anionic, non-ionic, cationic, ampholytic, zwitterionic and/or
semi-polar non-ionic surfactants. Preferred enzymes include but are not limited to
amylase, protease, lipase and mannanase. Oxygen or chlorine derived bleaches may be
combined with said surfactants, in addition to suitable liquid biocides to inhibit mould and
bacterial growth at the particle surface.
[0055] Additional components may be added to the particle cleaning agent in order to
provide chemical stability and dissolution, with the balance of the formulation being made
up with water. Said additional components may optionally include builders, chelating
agents, dispersants, enzyme stabilizers, catalytic materials, bleach activators, polymeric
dispersing agents, anti-redeposition additives, perfumes, optical brighteners, clay soil
removal agents, suds suppressors, dyes, structure elasticizing agents, carriers,
hydrotropes, processing aids and/or pigments.
[0056] As stated, examples of suitable surfactants may be selected from non-ionic and/or
anionic and/or cationic surfactants and/or ampholytic and/or zwitterionic and/or semi-polar
nonionic surfactants. The surfactant may be present at a level of from about 0.1% to about
99.9% by weight of the particle cleaning agent composition, but is usually present from
about 1% to about 80%, more typically from about 5% to about 35%, or from about 5% to
30% by weight of said particle cleaning agent composition.
[0057] The particle cleaning composition optimally also includes one or more detergent
enzymes which provide cleaning performance benefits. Examples of suitable enzymes
include, but are not limited to, hemicellulases, peroxidases, proteases, other cellulases,
other xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases,
reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, [beta]-glucanases, arabinosidases, hyaluronidase,
chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination may
comprise a mixture of enzymes such as protease, lipase, cutinase and/or cellulase in
conjunction with amylase.
[0058] Optionally, enzyme stabilisers may also be included amongst the cleaning
components. In this regard, enzymes for use in detergents may be stabilised by various
techniques, for example by the incorporation of water-soluble sources of calcium and/or
magnesium ions in the compositions.
[0059] The particle cleaning composition typically also includes one or more oxidising
agents/bleach compounds and associated activators. Examples of such bleach
compounds include, but are not limited to, peroxygen compounds, including hydrogen
peroxide, inorganic peroxy salts, such as perborate, percarbonate, perphosphate,
persilicate, and monopersulphate salts (e.g. sodium perborate tetrahydrate and sodium
percarbonate), and organic peroxy acids such as peracetic acid, monoperoxyphthalic acid,
diperoxydodecanedioic acid, N,N'-terephthaloyl-di(6-aminoperoxycaproic acid), N,N'-
phthaloylaminoperoxycaproic acid and amidoperoxyacid. Bleach activators include, but
are not limited to, carboxylic acid esters such as tetraacetylethylenediamine and sodium
nonanoyloxybenzene sulfonate. Chlorine based bleaches (e.g. sodium hypochlorite) may
also be used.
[0060] Suitable builders may be included in the formulations and these include, but are
not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates,
alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates,
polycarboxylate compounds, ether hydroxypolycarboxylates, copolymers of maleic
anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic
acid, and carboxymethyl-oxysuccinic acid, various alkali metal, ammonium and substituted
ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and
nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid,
oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethyloxysuccinic acid, and soluble salts thereof.
[0061] The particle cleaning agent formulation may also optionally contain one or more
copper, iron and/or manganese chelating agents.
[0062] Optionally, the said formulation can also contain dispersants. Suitable watersoluble
organic materials are the homo- or co-polymeric acids or their salts, in which the
polycarboxylic acid may comprise at least two carboxyl radicals separated from each other
by not more than two carbon atoms.
[0063] Suitable anti-redeposition additives are physico-chemical in their action and
include, for example, materials such as polyethylene glycol, polyacrylates and carboxy
methyl cellulose.
[0064] Optionally, the particle cleaning agent may also contain perfumes. Suitable
perfumes are generally multi-component organic chemical formulations, a typical example
of which is Amour Japonais supplied by Symrise® AG.
[0065] Appropriate optical brighteners for use in said particle cleaning agent formulations
fall into several organic chemical classes, of which the most popular are stilbene
derivatives, whilst other suitable classes include benzoxazoles, benzimidazoles, 1,3-
diphenyl-2-pyrazolines, coumarins, 1,3,5-triazin-2-yls and naphthalimides. Examples of
such compounds include, but are not limited to, 4,4'-bis[[6-anilino-4(methylamino)-1 ,3,5-
triazin-2-yl]amino]stilbene-2,2'-disulfonic acid, 4,4'-bis[[6-anilino-4-[(2-
hydroxyethyl)methylamino]-1 ,3,5-triazin-2-yl]amino]stilbene-2,2'- disulphonic acid,
disodium salt, 4,4'-Bis[[2-anilino-4-[bis(2-hydroxyethyl)amino]-1 ,3,5-triazin-6-
yl]amino]stilbene-2,2'-disulfonic acid, disodium salt, 4,4'-bis[(4,6-dianilino-1 ,3,5-triazin-2-
yl)amino]stilbene-2, 2 -disulphonic acid, disodium salt, 7-diethylamino-4-methylcoumarin,
4,4'-Bis[(2-anilino-4-morpholino-1 ,3,5-triazin-6-yl)amino]-2,2'-stilbenedisulfonic acid,
disodium salt, and 2,5-bis(benzoxazol-2-yl)thiophene.
[0066] The methods of the present invention may be used in the context of either small
or large scale batchwise or continuous processes and find application in both domestic
and industrial cleaning processes.
[0067] The invention will now be further illustrated, though without in any way limiting the
scope thereof, by reference to the following examples.
Examples
Example 1
[0068] Two fabric cleaning cycles were carried out using an apparatus as described in
WO-A-201 1/09881 5. This apparatus was based on a 50 kg Sea Lion industrial washerextractor,
modified to run with polymeric particles and, hence, it additionally comprised a
second chamber, pumping means, separating means, and rotatably mounted cylindrical
cage, as described in WO-A-201 1/09881 5. The polymeric particles were polyethylene
terephthalate (polyester) grade 110 1E, as supplied by INVISTA, Gersthofen, Germany.
The mass of particles in the apparatus was 50 kg. Both fabric washing cycles cleaned
very highly soiled car mechanics' overalls - 20.8 and 20.0 kg washloads respectively, as
supplied by Watford Launderers, London, UK. The cycles were both run at wash
temperatures of 65°C, with a 35 minute wash, followed by three rinses each of 10 minutes,
whilst using the following fabric cleaning agents, added sequentially throughout the fabric
cleaning cycle as shown:
a) 465.0 g Selox Mild - Christeyns, Bradford, UK (surfactant, added at the start of the
wash);
b) 8.4 g Antifoam RD Emulsion - DOW Corning, Barry, UK (antifoaming agent, added
at the start of the wash);
c) 223.2 g Mulan 200S - Christeyns (surfactant booster, added at the start of the
wash);
d) 231 .9 g Metajet Ultra - Christeyns (sodium hydroxide solution, 15-30% aqueous,
added after 10 minutes of the wash);
e) 16.8 g Antifoam RD Emulsion - DOW Corning (added after 10 minutes of the
wash);
f) 258.4 g Sodium Hypochlorite - Christeyns (sodium hypochlorite solution, 14-15%
aqueous, added after 20 minutes of the wash);
g) 100.0 g of Jetstream Jetsour - Christeyns (sodium bisulphite solution 15-30%
aqueous, added during the first rinse); and
h) 5.0 g Leucophor BMB Liquid - Vision Chemicals, Leeds, UK - (optical brightening
agent, 50% aqueous, added during the final rinse).
[0069] The water consumption of these fabric cleaning cycles was 176 litres each (8.5
and 8.8 litres/kg of washload respectively), and the power consumption was 13.3 kWh
each (0.64 and 0.67 kWh/kg respectively). There were very few polymeric particles left in
the washload at the end of the process, and the cleaning and deodourising of the
washload in general were excellent. The fabric cleaning agent dosages, the water
consumption and the power usage were all significantly less than those observed with the
corresponding conventional aqueous processes.
[0070] Each of these fabric cleaning cycles liberated approximately 1 kg of soil into the
washing apparatus (2 kg in total), thereby necessitating a polymeric particle cleaning cycle.
This was carried out according to the procedure previously described.
[0071] At the commencement of the polymeric particle cleaning cycle the apparatus
contained no washload, and the polymeric particles to be cleaned were held with an
amount of water ( 1 : 1 w/w) in the second chamber of the apparatus. This water was 67%
of the residual rinse water used in the previous fabric washing cycles. The polymeric
particles and water were then pumped by pumping means to the separating means, from
where the polymeric particles were transferred to the rotatably mounted cylindrical cage of
the apparatus. The water passing through the separating means was returned to the
second chamber. Pumping continued until the polymeric particles were essentially
removed from the second chamber.
[0072] At that stage of the process, the cage was held in a stationary position in order to
retain the polymeric particles. The perforations in the wall of the rotatably mounted
cylindrical cage allowed some polymeric particles to fall back into the second chamber, but
the number doing so was very small, as the ratio of the perforation diameter to that of the
particles was only slightly greater than 1 (5 mm perforations and 2.1 mm polymeric
particles, so the ratio was 2.4), and the action of pumping the polymeric particles into the
cage ensured that these quickly accumulated, thereby preventing further flow of particles
through the perforations. Pumping continued until transfer of the polymeric particles into
the cage was complete.
[0073] The polymeric particle cleaning agent was diluted in fresh water ( 100.0 g of
cleaning agent in -30 litres of water in the dosage means of the machine), and introduced
directly onto the particles in the cage, by using spray means through the access means at
the front of the cage, so as to provide more uniform coverage of the particles. The particle
cleaning agent formulation was as shown in Table 1.
TABLE 1 Particle Cleaning Agent Formulation
[0074] The pumping means was then used to circulate the polymeric particles, water and
particle cleaning agent into the now rotating cage, such that the fluids and a quantity of the
particles were continually exiting through the perforations in the cage wall. The process of
circulating the particles, water and particle cleaning agent from the second chamber, via
pumping means and separating means, to the rotating cage, and back to the second
chamber, then continued throughout the particle cleaning cycle. The water used was
heated to 45°C in order to further improve cleaning performance, and the treatment was
carried out for a duration of 15 minutes.
[0075] Following this part of the process, the particles were again pumped into the cage
via the separating means, the cage once again being held stationary. The water which
returned to the second chamber from the separating means during this transfer contained
the soil liberated from the particles, and so it was drained away and replaced with fresh
water. The rotatably mounted cage was once more caused to rotate, and the polymeric
particles were allowed to fall back into the second chamber.
[0076] At the conclusion of the polymeric particle cleaning process, the apparatus was
ready to begin again the process of fabric washing as described above. The next such
cycle cleaned 20.0 kg of white table linen, again as supplied by Watford Launderers,
London, UK. This cycle was carried out at ambient temperature (-20 °C), with a 35 minute
wash, followed by three rinses each of 10 minutes, using the following fabric cleaning
agents, added sequentially throughout the fabric cleaning cycle as specified:
a) 930.0 g Selox Mild - Christeyns, Bradford, UK (surfactant, added at the start of the
wash);
b) 16.8 g Antifoam RD Emulsion - DOW Corning, Barry, UK (antifoaming agent,
added at the start of the wash);
c) 49.6 g Mulan 200S - Christeyns (surfactant booster, added at the start of the
wash);
d) 347.9 g Metajet Ultra - Christeyns (sodium hydroxide solution, 15-30% aqueous,
added after 10 minutes of the wash);
e) 8.4 g Antifoam RD Emulsion - DOW Corning (added after 10 minutes of the wash);
f) 258.4 g Sodium Hypochlorite - Christeyns (sodium hypochlorite solution, 14-15%
aqueous, added after 20 minutes of the wash);
g) 100.0 g of Jetstream Jetsour - Christeyns (sodium bisulphite solution 15-30%
aqueous, added during the first rinse); and
h) 5.0 g Leucophor BMB Liquid - Vision Chemicals, Leeds, UK - (optical brightening
agent, 50% aqueous, added during the final rinse).
[0077] The water consumption for these fabric cleaning cycles was 170 litres (8.5
litres/kg of washload), and the power consumption was 1.6 kWh (0.08 kWh/kg). There
were very few polymeric particles left in the washload at the end of the process, and the
cleaning of the washload overall was excellent. Once again, the fabric cleaning agent
dosages, the water consumption and the power usage were all significantly less than
observed with the corresponding conventional aqueous process.
[0078] Significantly however, there was no carry over of soil from the preceding two
washes of mechanics overalls, thereby proving the efficacy of the polymeric particle
cleaning cycle run between the fabric washes.
Example 2
[0079] The efficacy of the particle cleaning formulation of Table 1 was further evaluated.
Thus, polymeric particles were pre-soiled by taking 12 kg of virgin 1101 E particles, and
adding to this the residual liquor from boiling 12 SBL2004 sebum cloths (WFK) in 3 litres of
water for 30 minutes, 700 g of tomato ketchup (Heinz), 200 g of instant coffee powder
(Morrisons, Value Range), 440 g of curry sauce (Morrisons, Value Range), 1200 g of
motor oil (Halfords) and, finally, a further 9 litres of water. This mixture was left at room
temperature for three weeks, and stirred for 30 minutes each day over that period.
[0080] Industry recognised stain sets (WFK Standard Industry/Commercial Laundry
Monitor PCMS-55_05-05x05) were used to record cleaning efficacy. Three of said stain
sets were added to 1 kg of dry cotton ballast (Whaleys, Bradford, UK), with 3 kg of presoiled
polymeric particles (INVISTA 0 E), and 9 litres of water, and this complete
washload was then heated to 60 ° and tumbled in a sealed metal drum for a period of two
hours. A lifter (metal ridge running axially along the inner surface of the drum) was used to
agitate the washload under tumbling (auto reversing every 10 minutes, at -40 rpm). The
resulting cleaning efficacy was recorded as Run BCP2/1 for each of the stains on the WFK
PCMS-55_05-05x05 stain sets, and averaged over the three sets used.
[0081] The exact fabric cleaning procedure of Run BCP2/1 was then repeated, with the
exception that the 3 kg of pre-soiled polymeric particles were cleaned using the particle
cleaning formulation of Table 1. Approximately 500 g of said formulation was diluted with
1 litre of water before being used to clean the particles in a large beaker at 45-50 ° for 30
minutes. The polymeric particles were continually stirred during this cleaning process.
After this cleaning procedure, the polymeric particles were filtered and rinsed with 500 ml
of clean water. The resulting cleaning efficacy was recorded as Run BCP3/1 for each of
the stains on the WFK PCMS-55_05-05x05 stain sets, and averaged over the three sets
used.
[0082] The exact fabric cleaning procedure of Run BCP2/1 was then repeated, with the
exception that virgin 1101 E particles were used. The resulting cleaning efficacy was
recorded as Run BCP4/1 for each of the stains on the WFK PCMS-55_05-05x05 stain
sets, and averaged over the three sets used.
[0083] It should be emphasised that in all three of the above runs (BCP2/1 , BCP 3/1 and
BCP4/1), no additional fabric cleaning agent was used, i.e. the cleaning recorded is that
which was achieved solely due to the action of the polymeric particles.
[0084] The level of cleaning was assessed using colour measurement. Reflectance
values of the WFK stain monitors were measured using a Datacolor Spectraflash SF600
spectrophotmeter interfaced to a personal computer, employing a 10° standard observer,
under illuminant D65, with the UV component included and specular component excluded;
a 3 cm viewing aperture was used. The CIE L* colour co-ordinate was taken for each stain
on the stain monitors, and these values were then averaged for each stain type, with
higher L* values show better cleaning. The results are shown in Table 2.
TABLE 2 Cleaning Results
[0085] From Table 2 it can be seen that the average regain of the cleaning performance
of the virgin 110 1 E particles due to the particle cleaning process ((BCP 3/1 L* - BCP2/1
L*)/(BCP 4/1 L* - BCP 2/1 L* )) is (74±7)%. Given the extreme nature of the particle pre-
0 soiling procedure used, this shows the particle cleaning formulation of Table 1 to be a very
efficient means of recovering particle cleaning performance, and thereby extending the
useable lifetime of the polymeric particles.
[0086] Throughout the description and claims of this specification, the words "comprise"
and "contain" and variations of them mean "including but not limited to", and they are not
5 intended to (and do not) exclude other moieties, additives, components, integers or steps.
Throughout the description and claims of this specification, the singular encompasses the
plural unless the context otherwise requires. In particular, where the indefinite article is
used, the specification is to be understood as contemplating plurality as well as singularity,
unless the context requires otherwise.
[0087] Features, integers, characteristics, compounds, chemical moieties or groups
described in conjunction with a particular aspect, embodiment or example of the invention
are to be understood to be applicable to any other aspect, embodiment or example
described herein unless incompatible therewith. All of the features disclosed in this
specification (including any accompanying claims, abstract and drawings), and/or all of the
steps of any method or process so disclosed, may be combined in any combination,
except combinations where at least some of such features and/or steps are mutually
exclusive. The invention is not restricted to the details of any foregoing embodiments.
The invention extends to any novel one, or any novel combination, of the features
disclosed in this specification (including any accompanying claims, abstract and drawings),
or to any novel one, or any novel combination, of the steps of any method or process so
disclosed.
[0088] The reader's attention is directed to all papers and documents which are filed
concurrently with or previous to this specification in connection with this application and
which are open to public inspection with this specification, and the contents of all such
papers and documents are incorporated herein by reference.

CLAIMS
1. A method for the treatment of polymeric particles recovered after use in cleaning
processes for soiled substrates, said method comprising treating said particles with a
particle cleaning agent.
2. A method as claimed in claim 1 wherein said particle cleaning agent comprises at
least one surfactant.
3. A method as claimed in claim 2 wherein said surfactant comprises at least one
anionic, non-ionic, cationic, ampholytic, zwitterionic and/or semi-polar non-ionic
surfactants.
4. A method as claimed in claim 1, 2 or 3 wherein said particle cleaning agent
comprises an aqueous liquor.
5. A method as claimed in any one of claims 1 to 4 wherein said particle cleaning
agent comprises at least one additional component selected from enzymes, oxidising
agents/bleaches and biocides.
6. A method as claimed in any preceding claim wherein said particle cleaning agent
additionally comprises one or more additional components selected from stabilisers,
wetting agents and solvents.
7. A method as claimed in any preceding claim wherein said particle cleaning agent
additionally comprises at least one additive selected from builders, chelating agents,
dispersants, enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing
agents, anti-redeposition additives, perfumes, optical brighteners, clay soil removal agents,
suds suppressors, dyes, structure elasticizing agents, carriers, hydrotropes, processing
aids and/or pigments.
8. A method as claimed in any preceding claim wherein said treatment is carried out
at a temperature of from 5 to 95°C.
9. A method as claimed in any preceding claim 14 wherein said process is carried out
for a duration of from 5 to 120 minutes.
10. A method as claimed in any preceding claim wherein said treatment is carried out
by sluicing a second chamber of a washing apparatus with clean water and cleaning said
polymeric particles in a rotatably mounted cylindrical cage of said apparatus.
11. A method as claimed in any preceding claim wherein said polymeric particles
comprise particles of polyalkenes, polyesters, polyamides or polyurethanes, or their
copolymers.
12. A method as claimed in claim 11 wherein said polyamide particles comprise nylon
beads.
13. A method as claimed in claim 12 wherein said nylon comprises Nylon 6,6
homopolymer having a molecular weight in the region of from 5000 to 30000 Daltons.
14. A method as claimed in any preceding claim wherein said polymeric particles are in
the shape of spheres, cubes or cylinders, and said particles are solid or hollow.
15. A method as claimed in claim 14 wherein said cylindrically shaped particles have
an average particle diameter in the region of from 1.0 to 6.0 mm and the length of said
particles is in the range of from 1.0 to 5.0 mm.
16. A method as claimed in any preceding claim wherein said particles have an
average mass in the region of from 1 to 50 mg.
17. A method as claimed in any preceding claim wherein said polymeric particles
comprise foamed or unfoamed polymeric materials and said polymers are either linear or
crosslinked.
18. A method for cleaning a soiled substrate, said method comprising the steps of:
(a) treating polymeric particles according to the method of any one of claims 1
to 17; and
(b) treating a moistened substrate with a formulation comprising a multiplicity of
said treated polymeric particles.
19. A method as claimed in claim 18 wherein said substrate comprises a plastics
material, leather, paper, cardboard, metal, glass or wood.
20. A method as claimed in claim 18 wherein said substrate comprises a textile fibre or
fabric which is a natural or synthetic fibre or fabric.
2 1. A method as claimed in claim 20 wherein said natural or synthetic fibre or fabric
comprises cotton, nylon 6,6 or a polyester.
22. A method as claimed in any one of claims 18 to 2 1 wherein said substrate is wetted
by contact with mains or tap water.
23. A method as claimed in claim 22 wherein said substrate is wetted so as to achieve
a substrate to water ratio of between 1:0.1 to 1:5 w/w.
24. A method as claimed in any one of claims 18 to 23 wherein the ratio of said
particles to substrate is in the range of from 0.1 : 1 to 10:1 w/w.
25. A method as claimed in any one of claims 18 to 24 wherein said treatment of a
moistened substrate with a formulation comprising a multiplicity of said treated polymeric
particles is carried out at a temperature of between 5° and 35°C.
26. A method as claimed in any one of claims 18 to 25 wherein said treatment of a
moistened substrate with a formulation comprising a multiplicity of said treated polymeric
particles is carried out for a duration of between 5 and 45 minutes.
27. A method as claimed in any one of claims 19 to 26 whenever used in a domestic or
industrial cleaning process.
28. A method as claimed in any preceding claim which comprises a batchwise process
or continuous process.
29. A formulation for cleaning a soiled substrate, said formulation comprising a
multiplicity of polymeric particles, wherein said particles have been treated with a particle
cleaning agent.