Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
1
Title: A reel
Description
The present invention relates to a reel for winding up and unwinding
filaments. Such a reel comprises a circular middle element and circular
flanges
positioned on either side of said middle element, wherein the diameter of said
middle
element is smaller than the diameter of said flanges, which middle element is
suitable for winding up and unwinding filaments.
Reels are used to store filaments and to later unwind the filaments
again. Every 3-D printer for instance requires a feed of material. A 3-D
printer usually
has a type of plastic material as feed, and this plastic material is supplied
on a reel.
This reel is mounted on a shaft on the 3-D printer, wherein the material is
heated by
the 3-D printer and a printing step then takes place. A 3-D printer makes a
three-
dimensional model, wherein the model is thus built up from very thin layers of
material. 3-D printing can be performed in many different ways, for instance
using
bioplastic, polyester and epoxy, but also photopolymer. In the fused
deposition
modelling (FDM) type method of 3-D printing melted plastic forms the basis of
the
model and is applied by means of a nozzle extruder. The starting material in
this
method of printing is usually a roll with yarns of plastic wound thereon, also
referred
to as filaments.
Reels for optical fibres for instance have been known for a long time.
Known from US patent No. 4,387,863 is a spool wherein preventing an undesired
bending of the optical fibre is particularly important. The spool disclosed in
this
American patent is made from two halves wherein the spool is cut in the axial
plane,
with a double flange at both ends. The two halves are attached to each other
with a
tongue and groove connection. Stated as a suitable material for the spool is a
semi-
rigid material, for instance EPS, this providing the option of clamping
connectors to
the end of the yarn. The above spool is therefore intended only for yarns with
a
connector on the end, and the geometry of the smaller inner flange is
therefore
specially configured for this purpose.
Further known from US patent No. 4,702,429 is a reel with which
electrical components are shipped. The reel disclosed in this US patent
consists of at
least five parts: one or more cores (manufactured from expanded polystyrene
(EPS))
with two flanges thereon (manufactured from cardboard) and two fastener parts
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
2
(manufactured from plastic). In the final configuration said reel is held
together by
the two fastener parts which are pressed into each other in mirrored manner,
wherein use is made of a barb and grooves in the opposite part. Different
shapes of
core can be used to make the reel suitable for the application, in particular
electrical
components.
Known from Japanese publication JP2008-120572 is a reel wherein a
material of a combination of PLA/PS (polylactic acid and polystyrene) is
applied to
manufacture the reel. For the desired conductivity a quantity of carbon powder
is
added, viz. 1-20% by weight, after which the intended reel is manufactured via
an
injection moulding process.
Japanese publication JP H05 41937 relates to a spool for fishing line,
which spool is manufactured from a degradable material, in particular ethylene
carbon monoxide copolymer. The spool according to this Japanese document does
not provide any possibility of reducing the empty volume or improved
stackability
wherein less than the whole construction volume is necessary. In addition,
said
copolymer cannot be deemed as the biodegradable material as stated in the
present
application. Ethylene carbon monoxide copolymer is a high-grade technical
plastic,
also known as polyketones, and have high tensile and impact strength, high
abrasion
resistance and outstanding chemical resistance.
Japanese publication JP 2008-120572 relates to a so-called conductive
reel assembled from a conductive resin composition comprising polystyrene,
conductive carbon powder and polylactic acid. Such a reel is applied for
winding up
electronic components. Said combination of materials, which consists of 10-60%
PLA, 1-20% conductive carbon powder and the for the rest of polystyrene, means
that this is not a biodegradable polymer. There is moreover no mention of the
density
whereby it can be assumed that the PLA is of regular form with a density of
> 1000 g/I.
European publication EP 1 792 941 relates to a flame-retardant resin
composition and articles, for instance a reel, manufactured on the basis of
the said
resin composition, wherein the resin composition consists of 5-95% by weight
of a
polylactic acid resin and of 95-5% by weight of an aromatic polycarbonate
resin and
at least one additive for the purpose, among others, of increasing
compatibility.
Further present is a flame-retardant agent, for instance a bromine or
phosphorus-
based compound. The addition of polycarbonate produces a material with a
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
3
composition which cannot be deemed a biodegradable polymer. There is moreover
no mention of the density whereby it can be assumed that the PLA is of regular
form
with a density of > 1000 g/I.
European publication EP 1 434 088 discloses a roll support member
composed of a thermoplastic resin, such as PE, PP or PS, a biodegradable
resin,
and a blend of paper or wood, viz. 0 to 95% by weight, preferably 1 to 51% by
weight, and a thermoplastic resin. This publication refers to a blend of
between
ideally 51-70% paper and 49-30% plastic, if wherein PLA is one of the
specified
options. There is however no single example which makes mention of polylactic
acid
resin. There is moreover no mention made of the density whereby it can be
assumed
that the PLA is of regular form with a density of > 1000 g/I.
Japanese publication JP H08 217338 relates to a foamed plastic part
applied to cover the outer side of a paper tube. The plastic layer thus
provides a top
layer onto which an adhesive tape can be wound. This layer of plastic will
itself
impart no or little stiffness and stability to the product but serves only as
covering of
the paper core in order to prevent direct contact. This is a straight cylinder
made up
of different materials, which materials cannot be deemed a biologically
degradable
polymer.
Japanese publication JP 2004-043071 relates to a core in which a tape
or sheet can be wound in order to protect the thin film or tape against
folding or
collapse during storage thereof. According to this Japanese document only the
outer
shell is composed of a foam-like material. No mention is moreover made of the
density whereby it can be assumed that the PLA is of regular form with a
density of >
1000 g/I.
International application WO 2016/031861 comprises a combination of
50-80 parts by mass of a non-crystalline resin selected from styrene resins,
polycarbonates, polyarylates, polyphenylene oxides and polysulfones, with 20-
50
parts by mass of PLA supplemented with 10-40 parts by mass of inorganic
filler.
Such a composition cannot be deemed a biodegradable polymer. There is moreover
no mention made of the density whereby it can be assumed that the PLA is of
regular form with a density of > 1000 g/I.
International publication WO 2006/094787 relates to a spool consisting
of two halves, each half of which is provided with a substantial area of
contact with
the other half, wherein it is stated that the connection is assembled such
that the
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
4
cores transpose into each other in a smooth form.
German publication DE 10 2005 010708 relates to a bayonet closure
making use of a thin-walled construction with resilient tongues which serve to
prevent reverse rotation of the closure, wherein the two halves are laid with
closed
contact surfaces against each other so that the core continues (substantially)
seamlessly and there is provision for a continuous surface on the inner side
of the
reel.
German publication DE 197 00 185 relates to the connection of
different types of spool halves wherein use is made of a corresponding contact
surface located at the division between the different types of halves. Use is
made on
this contact surface of a relatively simple tongue and groove connection
specifically
designed for a thin-walled product with associated material choice. There is
also
provision for a continuous surface on the inner side of the spool and the
winding
surface is continuous.
German publication DE 40 01 250 relates to a to a reel divisible into
two non-identical halves with a cylindrical press fit as connecting method,
wherein
there is also a provision for a continuous surface on the inner side of the
reel and the
winding surface is continuous.
There are a number of aspects which are an important factor in the
transport of reels from manufacturer to end user. One aspect is the reuse of
the reel.
Particularly in the case of end users using a high volume of reels it is
desirable that
the weight per reel is kept as low as possible. The costs of transporting the
reels can
be minimized with such a manner of use. It is also desirable that the reels
can be
reused in effective manner after use. With recycling in mind it is preferred
here that
the reel comprises as few different materials as possible. It is also
desirable that the
reels take up as little space as possible before assembly thereof takes place.
This
also has a favourable effect on the costs of transporting the reels to the
manufacturer which ultimately provides the reels with the desired filaments.
A drawback of for instance the reel known from the above stated US
patent No. 4,702,429 is that the fixed parts of this reel consist of various
different
materials, viz, cardboard and plastics, wherein only the variable core is made
from
an EPS foam.
Another observation relates to the spool known from the above stated
US patent No. 4,387,863 wherein because of the field of application, namely
wires
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
with connectors on the end, a specific dividing and attaching method is used
in
combination with a semi-rigid material, for instance EPS.
An object of the present invention is to manufacture a reel for winding
up and unwinding filaments, which reel has a low weight per volume.
5
Another object of the present invention is to manufacture a reel for
winding up and unwinding filaments, which reel is manufactured from a
biodegradable material.
Yet another object of the present invention is to manufacture a reel for
winding up and unwinding filaments, which reel, before arranging of filaments
thereon takes place, is easily stackable whereby little volume is taken up and
transport costs are limited to a minimum.
The present invention thus relates to a reel for winding up and
unwinding filaments, comprising a circular middle element, circular flanges
positioned on either side of said middle element, wherein the diameter of said
middle
element is smaller than the diameter of said flanges, which middle element is
suitable for winding up and unwinding filaments, characterized in that said
middle
element and flanges are manufactured from a biodegradable polymer.
One or more of the stated objectives are fulfilled by applying such a
reel. The application of a biodegradable polymer makes it possible for the
reel to be
disposed of in an environmentally-friendly manner after use. No residual
product is
created which is sent for instance to an incinerator or taken away to a
landfill site.
The application of a biodegradable polymer has the result that there is no
adverse
environmental impact. The material applied according to the present invention
provides a distinct weight-saving and is itself responsible for the geometry
and the
structural integrity of the reel. This is in contrast to the above discussed
prior art
wherein either a regular (non-foamed) PLA, i.e. PLA in regular form with a
density of
> 1000 g/I, is applied or a foamed plastic is used for only a part of the
product where
the specific properties of the foam are desired, and the foam does not
therefore
provide for the structural integrity.
The said biodegradable polymer is preferably selected from the group
of polylactic acid, such as 99.5% pure PLLA or PDLA, copolymers of L-lactic
acid
with 0.5-7% D-lactic acid, starch foam and/or blends of 5-40% PLA with a
remaining
quantity of additional components consisting of the group of starch, PBS,
PBAT,
PHA, PHB, PVA and PVAc or combinations thereof and with optional addition of
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
6
colouring agents, nucleants, compatibilizing agents such as Joncryl
(trademark,
marketed by BASF) styrene acrylate resins, in usual quantities.
Polylactic acid (PLA) is a renewable biodegradable material and is a
collective term for polymers on the basis of lactic acid monomers, wherein
depending
on the composition the structure of polylactic acid can vary from completely
amorphous to semi-crystalline or crystalline. Polylactic acid can be obtained
from
milk products or from for instance maize. Lactic acid is the monomer of which
polylactic acid is composed and this monomer occurs in two stereoisomers, viz.
L-
lactic acid and D-lactic acid. Polylactic acid thus comprises a certain
proportion of L-
lactic acid monomers and a certain proportion of D-lactic acid monomers. The
ratio
of the L- and D-lactic acid monomers in polylactic acid determines the
properties
thereof. Reference is also made to a D value or D-content. This represents the
percentage of D-lactic acid monomers in the polylactic acid. Polylactic acid
commercially available at the moment has a ratio L:D of 100:0 to 75:25, in
other
words a D-content of 0 to 25%, or between 0 and 0.25. When polylactic acid
contains
more than about 12% D-lactic acid it can no longer crystallize and is
therefore
completely amorphous. When the D-content is a maximum of 5%, it is referred to
as
semi-crystalline polylactic acid. The crystallinity of the polylactic acid can
be
determined by means of differential scanning calorimetry (DSC). Semi-
crystalline is
understood to mean that the polymer can crystallize and can also melt. It can
thus be
stated that the lower the D-content, the higher the crystallinity of the
polylactic acid.
The D-content is generally determined by a known method, such as a so-called R-
lactate determination using gas-liquid chromatography (GLC) following complete
hydrolysis of the polymer. Another standard method is determination via
optical
rotation (measured in chloroform using a Jasco DIP-140 polarimeter at a
wavelength
of 589 nm).
The present inventors have found that a reel manufactured from
polylactic acid can be deemed a reel which is renewable and the raw material
of
which is not scarce, and wherein the application thereof has no adverse
effects on
nature and environment. A reel according to the present invention in the
embodiment
as foam particularly has a density of up to 100 g/I, this value being at least
10 times
lighter than a reel obtained from an injection moulding process using ABS, PC
or
HIPS with density greater than 1000 g/I.
The term "manufactured from" applied in the present invention can be
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
7
interpreted in an embodiment as "wholly manufactured from". This means that
the
material is composed only of biodegradable polymer. No other polymers are
therefore present which can be deemed as non¨biodegradable. Reference can be
made in this respect to the above discussed literature references wherein for
instance ethylene carbon monoxide polymer, polystyrene, polycarbonate are
applied,
which materials can be deemed non-biodegradable. As already stated in the
present
application, it is indeed possible for combinations of biodegradable polymers
to be
applied in the present reel. Another difference relative to the above
discussed
documents is that the reels referred to therein are made via injection
moulding, while
the present reel is essentially different because the reel is manufactured on
the basis
of foamed beads and there is a reduction in weight. The present reel is
further
distinguished in that the foamed beads are made from PLA, thereby resulting in
a
completely biodegradable reel. There is no question here of a blend wherein
only a
part of the reel is degradable. The present inventors have further established
that
there is in principle a good compatibility between the present reel and the
yarn
placed around it, since PLA is used in both cases. There is therefore the
option of
processing the entity of reel and yarn in the same manner at end of life
(recycling,
composting).
The present inventors have found that polylactic acid foam has good
properties making the material suitable for processing to a reel. The
polylactic acid
which can be applied in such a reel according to the present invention can for
instance be selected from the group consisting of semi-crystalline polylactic
acid,
amorphous polylactic acid and a blend thereof. It is also possible to blend
the
polylactic acid with other (biodegradable) polymers. Examples hereof are a
copolyester of butanediol, adipic acid and terephthalic acid (trade name
Ecoflex from
BASF), starch paste and starch.
In an embodiment of the present invention the reel comprises polylactic
acid fibres, polylactic acid foam or combinations thereof. Because of their
structure
such forms of polylactic acid have good properties for processing to a reel.
It is
further possible for the reel to comprise recycled polylactic acid. Recycling
polylactic
acid reduces the impact on the environment. The recycled polylactic acid can
for
instance come from packagings or old reels.
During forming of foamed moulded parts based on particulate
expandable polylactic acid it is of great importance that the fusion between
the
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
8
individual particles is sufficient to obtain a product which does not
disintegrate into
the individual particles under a slight load. The process conditions are also
very
important. In view of the limited thermal stability of polylactic acid when
compared to
petrochemical polymers it is of great importance that proper fusion is
realized even
under mild process conditions.
In a specific embodiment a sufficient fusion can be achieved under
mild process conditions when particulate expandable polylactic acid is
provided with
a coating. It should be noted here that the foamed moulded part can be
obtained with
two different methods. Either the particulate expandable polylactic acid is
coated and
.. then foamed in one step and formed into a foamed moulded part, or the
particulate
expandable polylactic acid is first pre-foamed, then coated and subsequently
formed
into the foamed moulded part. The coating can thus be applied directly onto
the
particles of polylactic acid or onto already pre¨foamed particles of
polylactic acid.
After the coating has been applied a blowing agent has to be added to the
particles
in order to make them expandable (again). In the case the coating is applied
to
already pre-foamed particles of polylactic acid there is found to be an
additional
advantage, namely that the diffusion of blowing agents from the pre-foamed
particles
decreases so that a more reliable and more robust process is obtained. By
making
use of a coating foamed moulded parts can be made with improved fusion between
the individual particles. This makes it possible to make moulded parts of a
lower
density with similar or improved strength and an excellent thermal stability,
particularly in the application as reel.
As suitable coatings can be mentioned: polyvinyl acetate, polyvinyl-
acetate-based polymer, polyvinyl alcohol, polycaprolactone, polyester,
polyester
amide, protein-based material, polysaccharide, natural wax or grease and
acrylate or
one or more combinations thereof. The coating can also be amorphous polylactic
acid, or a combination thereof with the other coatings. Examples of a coating
based
on polyvinyl acetate and polyvinyl-acetate-based polymer are Vinnex and
Vinnapas
polymers from Wacker Chemie or Epotal from BASF. The coating on the basis of
the
.. protein-based material is preferably selected from the group consisting of
gelatin,
collagen, casein and soy protein and one or more combinations thereof. The
polysaccharide-based coating is preferably selected from the group consisting
of
cellulose, cellulose derivative, starch, starch derivative, chitosan,
alginate, pectin,
carrageen, gum arabic and gellan gum. The coating based on natural wax or
grease
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
9
is preferably selected from the group consisting of beeswax, carnauba wax,
candelilla wax, paraffin wax, polyethylene wax, fatty acid, monoglyceride and
shellac.
The density of the said biodegradable polymer preferably lies in the
range of 10 g/I and 100g/I, in particular between 15 g/I and 60 g/I. The shake
density
of non-pre-foamed particles of polylactic acid according to the present
invention
preferably lies between 700 g/I and 1000 g/I. The present inventors have
established
that said density gives particularly good results in the forming of the final
reel.
It is particularly desirable that said biodegradable polymer complies
with the composting standard EN13432. Products specified as compostable
materials are biodegradable within the norms laid down by EN13432. This
European
standard describes the period (three months), the conditions (industrial
composting
facility) and the permitted residual fractions.
From the viewpoint of storage and simplicity of manufacture,
particularly in respect of the moulds applied in the production process, it is
desirable
that said reel is made up of two identical halves, both of which halves are
connected
to each other using a bayonet closure in order to obtain the intended reel.
The intended reel thus consists of two identical halves connected to
each other with a bayonet closure. The two halves, viz, the connecting bayonet
closure, are safeguarded against uncoupling by a ring arranged around the core
in
the end flange (retaining groove). The present reel can thus be deemed a
divisible
reel with a continuous core and continuous surface.
The present invention thus relates to divisible reels consisting of two
identical and nestable halves, wherein the coupling between the two parts is
realized
by means of a bayonet closure and wherein the inner side of the flanges is
also
provided with a groove for receiving a core sleeve therein. The said unique
form of
the present closure has arisen from the limitations imposed by the choice of
material.
The structure of the inner hole is also the result of this choice and the
present
inventors have nevertheless managed, despite the material rules, to create a
continuously supported surface.
The present invention will be further elucidated hereinbelow on the
basis of a number of examples. These examples serve only by way of elucidating
the
present invention.
Figure 1 shows an embodiment of a reel for winding up and unwinding
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
filaments according to the present invention.
Figure 2 shows an embodiment of a sub-element of a reel for winding
up and unwinding filaments according to the present invention.
Figure 3 shows an embodiment of a sub-element of a reel for winding
5 up and unwinding filaments according to the present invention.
Figure 1 shows an embodiment of a reel 10 for winding up and
unwinding filaments (not shown) according to the present invention. The reel
10
comprises a circular middle element wherein circular flanges 1, 2 are
positioned on
either side of said middle element. The diameter of the middle element is
smaller
10 than the diameter of the circular flanges 1, 2, wherein the middle
element is suitable
for winding and unwinding of filaments. The reel 10 is wholly manufactured
from a
biodegradable polymer.
Figure 2 shows schematically a sub-element 20 of a reel 10 for winding
up and unwinding filaments according to the present invention. The sub-element
10
is embodied as a circle wherein flange 1 has a rim 5. Such a rim 5 is
desirable from
the viewpoint of mechanical properties and also provides the option that the 3-
D
printing yarn or filament remains on the reel 10 after being wound up. The
middle
element 3 is provided with means 4 for realizing a bayonet closure. In order
to
assemble a reel 10 two sub-elements 20 are connected to each other using said
bayonet closure. When thus assembled, a wide middle element 3 is created which
serves as surface for winding 3-D printing yarn or filament thereon. During
use of the
reel 3 the reel is mounted on a shaft on the 3-D printer (not shown), wherein
the
material of the 3-D printing yarn or filament is heated by the 3-D printer and
a
printing step then takes place. The sub-element 20 is manufactured wholly from
a
biodegradable polymer.
Shown in figure 3 is an embodiment of a sub-element 30 of a reel 10
for winding up and unwinding filaments according to the present invention. The
sub-
element 30 is embodied as a circle wherein the flange 1 has a rim 5. Located
in the
centre of the sub-element 30 are means 6 for realizing a bayonet closure. In
order to
assemble a reel 10 two sub-elements 30 are connected to each other using said
bayonet closure. When thus assembled, a wide middle element is created which
serves as surface for winding 3-D printing yarn or filament thereon. It is
possible in a
specific embodiment to combine the sub-element 20 with the sub-element 30 to
form
a reel. The sub-element 30 is manufactured wholly from a biodegradable
polymer. In
CA 03021527 2018-10-18
WO 2017/183976 PCT/NL2017/050252
11
figure 3 profile ejectors are shown schematically with reference numeral 7 and
printed/press-out fillers with reference numeral 8.
Example 1
A reel for winding 3-D printing yarn or filament was manufactured using
EPS with a diameter of 0.7-1.0 mm and a foamed density of 60 g/I. Grains of
the
Styrex 710R type were pre-expanded at a temperature of 110 C in a conventional
pre-expander to 55 g/I and, after 24 hours standing, a moulding step was
performed
in an aluminium mould using steam at a temperature of 110 C. The final product
has
a moulded density of 60 g/I.
Example 2
A reel for winding 3-D printing yarn or filament was manufactured using
BioFoam with density of 60 g/I. Applied as starting material were BF710
Synterra
green bio-beads, with a size of 0.7-1.0 mm, marketed by Synbra Technology.
Said
beads were pre-impregnated with 9% CO2, then expanded to 55 g/I using hot air
at a
temperature of 90 C as heating medium, and provided with a coating in a
quantity of
5% (m/m), namely Vinnex 2510 - marketed by Wacker of Burghausen (Germany) -
and subsequently shaped into a 3-D reel at a shaping temperature of 90 C in
order
to obtain a 60 g/I 3-D reel. Said reel was suitable for winding up a quantity
of 1 kg
3 mm PLA (95%)/PHA (5%) filament.
Example 3
A 3-D filament reel as referred to in Example 2 was manufactured
using a composition of a foam of 20% PLA and 80% PBAT. Said composition was
impregnated with 9% CO2 and then expanded to 55 g/I and subsequently shaped
into
a 3-D reel at a shaping temperature of 90 C in order to obtain a 60 g/I 3-D
reel.
