METHOD FOR MAKING MASTERBATCH The present invention relates to a process for producing

a colouring agent for colouring a polymer, and in particular to a process for producing a master
batch for use in extrusion processes and the like.

The development of polymer chemistry and its subsequent application to the production of
industrial and household articles is one of the great success stories of the 20th century. The result
is that an enormous range of articles are now produced from plastics materials.

Some of these were previously produced from alternative materials, and the production of some
has only been possible because of the development of polymer chemistry.

Despite the fact that this technology is more than a century old, the scale of production of these
articles is such that research into new and improved polymers and methods of production
continues apace.

The natural colour of most plastics materials is rather unattractive and variable, and accordingly a
colouring agent has traditionally been added to the plastics material in order to produce a finished
article of uniform colour. When the aesthetic appearance of the article is not particularly important
(for example in the production of dustbins or industrial components), then the article is often
coloured black. However, it is possible to produce the full range of colours simply by varying the
colouring agent in order to meet consumer demand.

The colouring agent is normally prepared by adding a dyestuff to a plastics material in order to
produce a small amount of intensely coloured plastics material, and then by mixing the intensely
coloured plastics material with a second plastics material (which may or may not be the same as
the first) when the second plastics material is being formed into the finished article. The intensely
coloured first plastics material is known as "masterbatch".

Black masterbatch is generally formed by mixing carbon black with an appropriate polymer and
optionally adding chalk dust as a filler in an extrusion machine. The components are heated,
mixed, extruded and pelletised to produce the masterbatch, which is then added in amounts of 0.1
to 25% by weight to the plastics material when it is being processed into the finished article (for
example in a moulding or extrusion process).

If it is desired to produce a masterbatch of a different colour, then an appropriately coloured

pigment is mixed with the polymer and chalk filler (normally without carbon black) and the process
is carried out as before.

Industry is always on the lookout for improved production processes, particularly in the field of
polymer chemistry with its large scale of production and the consequently large cost savings
available.

EP 0322555 (General Electric Company) discloses a method for colouring thermoplastic polymer
resins using a masterbatch which is formed from a colorant such as carbon black and a
polyetherimide ester elastomer. A wide variety of inorganic and organic colorants are disclosed.
The masterbatch may be manufactured on high intensity high shear equipment such as
compounding extruders, two-roll compounding mills and in Banbury mixers. <BR> <BR> <P>WO
79/00406 (Akesson et al. ) discloses a method for the preparation of a masterbatch to be added to
a thermoplastic resin. The masterbatch is in the form of a colourant including colour pigment
particles as an additive dispersed in a vehicle.

JP 08003322 (Canon KK) discloses compositions for colouring plastics comprised of thermoplastic
polymers and pigments. The compositions give mouldings without unevenness or density
difference of colour.
According to a first aspect of the present invention, there is provided a process for producing a
colouring agent for colouring a polymer, comprising the step of mixing a plastics material and
waste print resin. Optionally, pure carbon black and low density polyethylene may be added.

Print resin is a specific product used by the print industry to create print automatically and at high
speed onto paper (or another substrate) without causing smudging.

Print resin is normally provided in powder form, and generally comprises at least some of the
following components: carbon black, ferrous oxide, carranba wax, styrene acrylic polymer,
polyester resin, zinc stearate, nigrazine dye and oxide fumerate powder. A variety of carrier
polymers may be included depending on the brand. Ferrous oxide, carbon black and nigrazine dye
are black colour enhancers, and one or two of the three may be omitted, depending on the shade
of black or brand of powder employed. If a different colour to black is required, then all three are
omitted, and a pigment of appropriate colour is added.

Without wishing to be constrained by theory, it is thought that print powder also includes a
component or number of components which stabilises the melting point of the composition. All
waste print powders investigated by the applicants (including waste print powders obtained from
Xerox, Canon, Ricoh, Hewlett-Packard and Osay) have a melting point close to 118°C.

As the temperature is raised above the melting point, the waste print powder hardens again.

Investigations have found that this solidification point is in all cases very close to 0. 75°C above the
melting point, i. e. 118. 75°C.

Print powder is normally provided in a sealed cartridge for use in computer printers and
photocopying machines. The cartridge may have a sliding door or the like which opens when the
cartridge is fitted into the printer in order to allow access to the waste print powder, and closes
when the cartridge is removed from the printer in order to prevent the escape of powder.

It is impractical to design a system which uses all of the powder in a cartridge and inevitably
somewhere in the region of 5% of the powder remains inaccessible in the cartridge when the
printer shows the cartridge as having expired.

Even though the amount of powder remaining in a spent cartridge is relatively small, the total
number of spent cartridges and therefore the total amount of waste powder produced by industry is
substantial and growing rapidly.

The powder left in expired cartridges is a waste product which is very difficult to dispose of. The
powder is so finely divided (with particle sizes being in the order of 15, um) that it tends to escape
from landfill sites and find its way to the water supply, with serious environmental consequences.
This is now of world-wide concern.

The inventive realisation of the present realisation is that this waste print powder can be used to
make masterbatch. Thus, a waste product which is extremely difficult to dispose of in an
environmentally friendly way can be employed in the production of an industrially useful product.

A substantial amount of surplus or imperfect waste print powder is produced by print

manufacturers, and often this is difficult or expensive for the manufacturer to dispose of.

Accordingly, the powder employed in the present invention may be obtained from spent cartridges
as described above, or may be obtained directly from the print manufacturer, who may have
supplies which could not otherwise be used in print cartridges. For example, waste powder for
printer cartridges must be produced with having narrow particle size distribution. Powder having
particles which are too small (in the order of 2 , um or less) or too large (in the order of 10 am or
more) cannot be employed in printer cartridges and is surplus to requirements. It is however
perfectly suitable for the purposes of the present invention.
The preferred proportion by weight of the components in the inventive process is as follows:
Plastics materials-preferably from 5 to 95%, more preferably at least from 20 to 50%, most
preferably about 25%.

Carbon black-preferably from 0.5 to 80%, more preferably from 20 to 40%, most preferably about
25%.

Waste print powder-preferably from 5 to 80%, more preferably from 25 to 50%, most preferably
about 40%.

The ratio of plastics material to carbon black depends on the particle size of the carbon black. Thus
the ratios of particularly preferred embodiments of the present invention are given in Table 1
below: TABLE 1 CARBON BLACK % % % DBP STRUCTURE CARBON BLACK PLASTICS
WASTE PRINT MATERIAL POWDER 170 20 35 45 137 22. 5 32. 5 45 115 25 30 45 70 30 25 45
65 32 23 45 55 35 20 45 The term"Carbon Black DBP Structure"refers to the grade of carbon black
and is a definition well known in the industry.

If these ratios are not adhered to, the likelihood is that: (1) the end product will be too brittle to be
effective (2) the product will overheat during the process and the mixture will oxidise (3) if oxidation
does occur the pigment transportation qualities of the product are reduced to below commercial
value.

It has been found that the use of waste print powder on its own results in an end product which is
too brittle to be effective.

The relative proportions of the various components is varied depending on how dark the
masterbatch is required to be (the so-called"cover"). For example, if heavier cover is required than
that given by the preferred proportions of 50% waste print powder, 25% carbon black and 25%
polymer, then 45% waste print powder, 30% carbon black and 25% polymer may be used. Ideally,
the polymer is included at 25% by weight or more, which prevents the final product becoming brittle
and difficult to handle during extrusion.

Other additives may be included to create and/or enhance the required end-product specification.

In order to produce a non-black colouring agent, the appropriate coloured pigment (e. g. coloured
waste print powder) is mixed with the plastics material in accordance with the invention. The
coloured powder may be supplemented with additional pigment and/or other additives, in order to
produce the desired final colour.

An effective masterbatch can be prepared by the following preferred process: 1. The components
are mixed loosely in a drum.

2. The components are transferred by a variable speed feeder at a defined rate to a mixer and
grinder where they are mixed, ground and amalgamated.

3. The resulting materials exit the pre-mixer in a rope form which is then fed by a time-sequenced
pusher device at a constant rate into an extruder.

4. The mixture is mixed and extruded as a series of strands.

In a preferred embodiment, the components are mixed together and heated in a mixing machine
such as a twin screw extruder, a single screw extruder, a two roll mill, or, preferably, a Farrel CP
machine, a Banbury mixer, or any suitable mixer.

It has been found that it is advantageous to keep the entrance into the mixer relatively cool in order
to avoid softening the waste print powder (which softening begins at about 90°C).
Keeping the entrance below about 90°C, preferably from 40 to 90°C and most preferably about
45°C, enables the waste print powder to be transported into a mixer in a stable condition. It is
particularly desirable to control this temperature carefully in the case of mixers other than Banbury
or Farrel CP machines. The advantage of using a Banbury or Farrel machine is that mixing of the
components is more thorough and the entrance temperature is not so critical.

Processing temperatures within the mixer are fairly flexible, but preferably range from 135 to 230°C
and are most preferably at about 150°C. At approximately 118°C, the waste print powder melts and
then very rapidly hardens as the temperature rises by another degree or so. It is therefore
necessary to use a mixer which is sufficiently powerful to grind the powder continuously to prevent
it from conglomerating and hardening. The mixer should be sufficiently powerful to mix the waste
print powder and the carbon black into the carrier resin homogeneously. It has been discovered
that the Banbury and Farrel machines are particularly effective at achieving this aim.

In a preferred embodiment, the components are mixed at a mixing rate of from 150 to 500 min-1,
preferably from 350 to 400 min-l.

Because the processing temperature tends to range from 135 to 230°C, heat is transferred from
the main body of the mixer to the mixer entrance. Accordingly, the mixer entrance may be
artificially cooled, for example by circulating cooled water in a jacket around the entrance, in order
to maintain the entrance at the temperatures outlined above.

The components are fed into the mixer until the maximum safe operational amperage is reached.
In the case of a Farrel CP 500, the maximum amperage is in the region of 90 to 95 amps and this
equates to a rate of addition of the mix of from 500 to 550 kg per hour.

The plastics material may be selected by a skilled person to match the plastics material which is to
be coloured by addition of the masterbatch. Suitably plastics material include polyethylene,
polypropylene, EVA, EEA, ABS, PVC or any other type of polymer.

After the components have been mixed to form the masterbatch, the masterbatch may be extruded
and divided into pellets for use in the colouring of a second plastics material.

In accordance with a second aspect of the invention, there is provided a colouring agent for
colouring a polymer which agent is obtainable by means of a process defined above.

In accordance with a third aspect of the invention, there is provided a process for forming a
coloured object from a plastics material, comprising the steps of mixing said plastics material with a
colouring agent obtainable by means of a process as defined above, and forming the coloured
plastics material into said object. The object may be formed by means of an extrusion or moulding
process.

The amount of masterbatch added to the plastics material generally varies from 1 to 25% by
weight. The precise amount will depend on the level of cover required, and from what the plastics
material is formed. For example, if the plastics material is clear, then a relatively low amount of
masterbatch is required (perhaps 1-2%) in order to produce a good level of cover. If however
plastics material is used which has been coloured white (with e. g. titanium dioxide), then perhaps
15-20% of masterbatch may be required in order to achieve the same level of cover. Cover is
usually assessed by eye and the components of the subsequent process adjusted accordingly.

In a fourth aspect of the invention, there is provided an object formed from a plastics material,
which material has been coloured by the addition of a colouring agent obtainable by means of a
process as defined above.

The invention will now be illustrated by means of the following examples.

Example 1 Carbon black, print powder from expired printer cartridges and manufacturer's waste
and polyethylene resin were weighed and loaded into a blender above an extruder in the following
amount: Carbon black-25% Print powder-50% Polyethylene-25% After being blended the mixture
was fed into a Farrel CP 500 mixer at a feed rate of from 350 to 550Kgph.

The entrance to the mixer as surrounded with a water-cooled jacket in order to maintain the
temperature at about 60 to 70°C.

The components were mixed at high pressure within the Farrel CP 500 at approximately 150°C
and at a mixing speed of from 350 to 400 revolutions per minute.

The resultant mix was discharged from the mixer in the form a continuous hot rope into a single
screw extruder. It was then pushed through a dye to form separate strands, which were fed into a
pelletiser where pellets were formed and cooled.

Example 2 The process of Example 1 was carried out except that the proportions of the
components were altered to the following in order to provide masterbatch with a heavier cover:
Carbon black-30% Waste print powder-45% Polyethylene-25% Machine settings are within
parameters as defined in Example 1.