(19)

*EP004368665A1*
(11) EP 4 368 665 A1
(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) International Patent Classification (IPC):

15.05.2024 Bulletin 2024/20 C08L 1/26 (2006.01) C08L 23/08 (2006.01)
C08L 29/00 (2006.01) C08L 29/04 (2006.01)
(21) Application number: 22207317.3 B32B 27/10 (2006.01) B32B 27/30 (2006.01)
B32B 27/36 (2006.01)
(22) Date of filing: 14.11.2022
(52) Cooperative Patent Classification (CPC):
(C-Sets available)
B32B 27/10; B32B 27/306; B32B 27/36;
C08L 1/08; C08L 1/26; C08L 29/04; C08L 91/06;
C09D 101/08; C09D 101/26; C09D 191/06;
B32B 2250/02; B32B 2250/03; B32B 2250/04;
B32B 2250/05; B32B 2255/10; (Cont.)

(84) Designated Contracting States: • GARCÍA MONTEAGUDO, Miguel

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB 46136 Museros
GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL Valencia (ES)
NO PL PT RO RS SE SI SK SM TR • AGREDANO,Isabel
Designated Extension States: 46136 Museros
BA Valencia (ES)
Designated Validation States: • BALKAU, Werner
KH MA MD TN 8762 Glarus-Süd/Schwändi (CH)

(71) Applicant: B&T Entwicklungs- und (74) Representative: Frei Patent Attorneys
Vermarktungsgesellschaft mbH Frei Patentanwaltsbüro AG
22297 Hamburg (DE) Hagenholzstrasse 85
8050 Zürich (CH)
(72) Inventors:
• MORENO LÓPEZ, Elena
46136 Museros
Valencia (ES)

(54) POLYMER COMPOSITION AND A MULTILAYER THEREOF

(57) The invention relates to a polymer composition layer comprising the polymer composition, wherein the
comprising a crosslinked mixture of at least a water-sol- first layer has an oxygen transmission barrier. The mul-
uble polymer and Polycaprolactone (PCL). The tilayer further comprises at least one second layer,
crosslinking of these components improves the water va- wherein second layer has a water vapor and/or humidity
por and/or humidity barrier properties of the polymer barrier. The second layer comprises a wax. The wax can
composition, while keeping chemical and mechanical be in particular a natural wax, in particular food-safe wax,
stability of the polymer composition. The invention also in particular bio-degradable wax, in particular bees wax.
relates to a multilayer, which comprises at least one first
EP 4 368 665 A1

Processed by Luminess, 75001 PARIS (FR) (Cont. next page)

 EP 4 368 665 A1

(52) Cooperative Patent Classification (CPC): (Cont.)

B32B 2255/26; B32B 2307/7244;
B32B 2307/7246; B32B 2307/7248;
B32B 2439/40; B32B 2439/70

C-Sets
C08L 29/04, C08K 5/092, C08L 67/04

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 EP 4 368 665 A1

Description

[0001] The invention relates to the field of polymer multilayer as described in the preamble of the independent claims.
[0002] Commercially established packaging materials for high-barrier food-applications pose increasing challenges
5 to recycling systems and end-of-life scenarios as sources of microplastics. Due to the high barrier requirements for
packaging certain types of food materials, conventionally used solutions are mostly multilayer systems made up of non-
biodegradable polymers and in addition often metallized surfaces. These multilayer systems cannot be recycled and
thus pose a high threat of natural ecosystems in increasing volume.
[0003] Alternative packaging is known from European patent application EP 22171579.0 or EP 22 171 641.8 showing
10 multilayer structures containing PVOH.
[0004] It is therefore an object of the invention to create an alternative polymer composition, multilayer containing a
polymer composition and the usage of the multilayer in packaging, in particular food packaging.
[0005] These objects are achieved by a multilayer and the usage of the multilayer as well as a packaging and/or a
layered structure comprising the multilayer according to the independent claims.
15 [0006] The invention relates to a polymer composition comprising a crosslinked mixture of at least a water-soluble
polymer and Polycaprolactone (PCL). The crosslinking of these components improves the water vapor and/or humidity
barrier properties of the polymer composition, while keeping chemical and mechanical stability of the polymer composition.
[0007] In an embodiment, the polymer composition is a food contact material. This means that the polymer composition
is allowed to have contact with food, e.g. in food packaging. The contact of the polymer composition with food does not
20 have any disadvantages for the food and/or the consumer.
[0008] In embodiments, the polymer composition (55) is at least one of bio-degradable and compostable, in particular
home compostable.
[0009] Bio-degradation in the context of this text means the breakdown of the polymers of multilayer by microorganisms.
Bio-degradability means that a material must have degraded to more than 90 percent to water, carbon dioxide (CO2)
25 and biomass and maybe mineral salts after a specified time under defined specific temperature, oxygen and humidity
conditions in the presence of microorganisms or fungi.
[0010] In the present text, "bio-degradable" may mean biologically degradable according to the European standard
EN 13432 (as of the end of 2021). In addition, or as an alternative, it may mean biologically degradable according to the
European standard EN 14995 (as of the end of 2021). Thus "bio-degradable" especially refers to "biologically degradable
30 according to EN 13432 and/or according to EN 14995.
[0011] In an embodiment, the polymer composition can be bio-degradable in at least one of soil, water, waste water.
[0012] As far as in the present text water-soluble polymers are mentioned, such water-soluble polymer may optionally
be (bio-)degradable in sewage treatment plants (aerobic biodegradability) in accordance with EN ISO 9888 (as of the
end of 2021); determined in accordance with the so-called Zahn-Wellens test, in particular at 20°C.
35 [0013] The term compostable refers to a bio-degradation under specific conditions.
[0014] In order for the multilayer, in particular the first layer and/or the second layer, to be compostable, at least the
following conditions can be fulfilled:

- at least 90% of the organic material must be verifiably bio-degraded in CO2 within 6 months;
40 - after 3 months of composting and subsequent screening through a 2 mm mesh sieve, no more than 10% residue
of the original mass may remain;
- there must be no negative effects on the composting process in general;
- no negative effect of the resulting composts on plant growth (agronomic test) and/or ecotoxicity test;
- the maximum concentration of heavy metals (Cu, Zn, Ni, Cd, Pb, Hg, Cr, Mo, Se, As) and florins must not be exceeded.
45
[0015] During composting the polymer composition can be decomposed. The polymer composition can be composted
and/or decomposed in a short time to carbon dioxide (CO2) and water (H2O) and biomass.
[0016] The polymer composition can be industrial and/or home compostable. The home compostability may not neg-
atively influence the industrial composting process.
50 [0017] In the present text, "compostable" or "home compostable" means compostable or home compostable according
to the European standard EN 13432 (as of the end of 2021) for packaging and/or according to the European standard
EN 14995 (as of the end of 2021) for plastics/synthetic materials. Compostable materials are always bio-degradable,
but not necessarily vice versa, meaning not all bio-degradable materials are compostable.
[0018] In embodiments, at least one of the following conditions is fulfilled:
55
- the water-soluble polymer is at least one of poly(vinyl alcohol) (PVOH), cellulose-ether polymer, Butenediol-Viny-
lalcohol-Copolymer (BVOH), and Ethylene-Vinylalcohol-Copolymers (EVOH);
- the water-soluble polymer is inter- and/or intramolecular crosslinked by natural and food-safe compounds.

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 EP 4 368 665 A1

[0019] In an embodiment, the water-soluble polymer is inter- and/or intramolecular crosslinked by citric acid with the
Polycaprolactone. The crosslinking of polycaprolactone with e.g. polyvinyl-alcohol via citric acid facilitates a synergy of
improving a barrier-performance in term of minimizing the oxygen transmission barrier, while keeping chemical and
mechanical stability of the polymer composition constant. This crosslinked system of PVOH and PCL in the polymer
5 composition provides excellent lamination properties and sealability to a paper base layer as well as to itself.
[0020] The invention relates to a multilayer, which comprises at least one first layer comprising a polymer composition
as described above, wherein the first layer has an oxygen transmission barrier. The multilayer further comprises at least
one second layer, wherein second layer has a water vapor and/or humidity barrier. The second layer comprises a wax.
The wax can be in particular a natural wax, in particular food-safe wax, in particular bio-degradable wax, in particular
10 bees wax. The wax enables to minimize the risk of migration of odours from and/or to the packaged goods. As the first
layer comprises the crosslinked polymer composition comprising poly vinyl alcohol (PVOH) and polycaprolactone (PCL).
The crosslinked composition improves the oxygen transmission barrier-performance, whilst keeping chemical and me-
chanical stability constant as compared to a non-crosslinked composition.
[0021] The wax-based second layer may also be called film. In embodiments, the wax-based second layer can be
15 coated evenly onto the first layer. The first layer might be a hydrophilic polymer-film. The second layer might be applied
without islanding or defects in the film, thus providing excellent water vapor and/or humidity barrier.
[0022] In embodiments, the multilayer has a water vapor and/or humidity barrier of a maximum of 15 g/m2 per day at
25°C and a relative humidity of 80%, in particular a maximum of 10 g/m2 per day at 25°C and a relative humidity of 80%,
in particular 3 g/m2 per day at 25°C and a relative humidity of 80%, in particular 2 g/m2 per day at 25°C and a relative
20 humidity of 80%. The excellent water vapor and/or humidity barrier are in particular provided by the wax included in the
second layer. This makes the multilayer suitable for packaging barrier-sensitive goods, such as coffee.
[0023] The polymer composition and/or the multilayer, in particular the first layer, can have an oxygen transmission
rate of a maximum of 3 cm3/m2 per day at room temperature (RT, room temperature = 23°C) and a relative humidity of
50% (relative humidity = r. h.), in particular the oxygen transmission rate can be maximal 1 cm3/m2 per day at room
25 temperature and a relative humidity of 50%, in particular maximal 0,2 cm3/m2 per day at room temperature (23°C) and
a relative humidity of 50%; in particular maximal 0,05 cm 3/m2 per day at room temperature (23°C) and a relative humidity
of 50%.
[0024] The oxygen transmission rate (OTR) is the steady state rate at which oxygen gas permeates through a film at
specified conditions of temperature and relative humidity. Values are expressed in cc/m2/24 hr in metric (or SI) units,
30 with cc being cubic centimetre being cm 3, m 2 being square metre, 24 hr being 24 hours being one day. The OTR in this
text is determined according to ISO 15105-2 (as of April 2022).
[0025] In embodiments, the second layer comprises an emulsifier. The emulsifier can be natural and/or food-safe.
The emulsifier can be at least one of mono- and di-glycerides.
[0026] The emulsifier enables the suspension of fat and water. This makes it possible that the second layer can be
35 applied as a rather homogenous layer on top of the first hydrophilic layer.
[0027] In an embodiment, the first layer comprises at least two sublayers, for example a first sublayer and a second
sublayer. Both sublayers can comprise a PVOH based polymer composition. The first sublayer can comprise poly vinyl
alcohol with adhesive properties. The first sublayer can be based on low-Tg & degree of hydrolysis (DH) PVOH. The
second sublayer can be water-soluble. The second sublayer can comprise the polymer composition, as described above,
40 as a crosslinked mixture comprising poly vinyl alcohol (PVOH) and polycaprolactone (PCL). In particular the second
sublayer can provide the oxygen transmission barrier (also called gas barrier) properties to the multilayer.
[0028] In embodiments, the first layer can be applied by co-extrusion, in particular by co-extrusion of the first sublayer
and second sublayer.
[0029] In embodiments, the layers of the multilayer are separable from each other. This allows for an individual recycling
45 of the layers of the multilayer. In embodiments, the layers of the multilayer can be separated from each other under the
conditions of the recycling process. In particular the layers are separable at a maximum temperature of 40 °C, in particular
of 38°C to the most, in particular of 35°C to the most, in particular of 30°C to the most, in an aqueous environment.
[0030] In embodiments, the multilayer is non-toxic. This enables the usage of the multilayer in connection with foods.
In particular the multilayer is non-toxic to human, in particular the multilayer is recognized as safe in food industry.
50 [0031] In embodiments, the multilayer is a food contact material. This means that the multilayer is allowed to have
contact with food, e.g. in food packaging. The contact of the multilayer with food does not have any disadvantages for
the food and/or the consumer.
[0032] In an embodiment, the multilayer, the polymer composition and/or at least the water-soluble polymer is at least
one of bio-degradable and compostable, in particular home compostable. While water-soluble polymers may be bio-
55 degradable, this is not necessarily the case for all water-soluble polymers. The water-soluble polymer of the multilayer
may be bio-degradable in addition to being water-soluble. Due to this the multilayer provides sufficient barrier properties
for example for sensitive food products, and which simultaneously is compatible with existing recycling streams. In
regions without such recycling streams or where landfill is common, the multilayer and/or the polymer composition is

4
 EP 4 368 665 A1

neutral to the environment and decomposed in short time into carbon dioxide (CO2) and water (H2O) as well as biomass.
[0033] In the present text, "bio-degradable" may mean biologically degradable according to the European standard
EN 13432 (as of the end of 2021). In addition, or as an alternative, it may mean biologically degradable according to the
European standard EN 14995 (as of the end of 2021). Thus "bio-degradable" especially refers to "biologically degradable"
5 according to EN 13432 and/or according to EN 14995.
[0034] In an embodiment, the multilayer, in particular the first layer and/or the second layer, can be bio-degradable in
at least one of soil, water, waste water.
[0035] As far as in the present text water-soluble polymers are mentioned, such water-soluble polymer may optionally
be (bio-)degradable in sewage treatment plants (aerobic biodegradability) in accordance with EN ISO 9888 (as of the
10 end of 2021); determined in accordance with the so-called Zahn-Wellens test, in particular at 20°C.
[0036] Due to this the multilayer provides sufficient barrier properties for example for sensitive food products, and
which simultaneously is compatible with existing recycling streams. In regions without such recycling streams or where
landfill is common, the multilayer is neutral to the environment and decomposed in short time into carbon dioxide (CO2)
and water (H2O) as well as biomass.
15 [0037] Multilayer and/or a polymer composition made of bio-degradable plastics according to the prior art sometimes
show low barrier performance, in particular against oxygen and water vapor, as well as low head deforming stabilities.
[0038] In an embodiment, the multilayer can be compostable, in particular home compostable. At least one of the first
layer and the second layer can be compostable, in particular home compostable.
[0039] In order for the multilayer, in particular the first layer and/or the second layer, to be home compostable, at least
20 the following conditions must be fulfilled:

- at least 90% of the material must have decomposed into water, carbon dioxide and biomass in a compost heap (at
approx. 30°C) within 6 months;
- neither organic pollutants nor heavy metals may enter the soil;
25 - the substances must not have any negative impact on the compost quality;
- the products can be disposed of in the garden compost and in the organic waste bin.

[0040] In embodiments, the multilayer comprises a third layer. The third layer can be applied on top of the second
layer. This further eliminates the risk of migration of odours from wax of the second layer to the packaged goods.
30 [0041] In embodiments, the third layer is similar to the first layer. This means that the third layer can have any of the
properties as described above for the first layer, but the properties of the first layer and the third layer do not have to be
identical. For example, the third layer can comprise a water-soluble polymer, wherein the polymer can be hydrophilic.
The third layer can be coated onto the (wax-barrier) second layer, also called second layer.
[0042] In an embodiment, the third layer comprises a crosslinked polymer composition comprising poly vinyl alcohol
35 (PVOH) and polycaprolactone (PCL), in particular as described above. The crosslinked polymer composition improves
the oxygen transmission barrier-performance. In an embodiment, he third layer can enable an aroma barrier for the
second layer, in particular for the wax. The third layer can also function as sealing promoter.
[0043] In an embodiment, the third layer comprises at least two sublayers, for example a first sublayer and a second
sublayer, similar as described above for the first layer. Both sublayers can comprise a PVOH based polymer composition.
40 [0044] The third hydrophilic layer can be compatible to the hydrophobic second layer in the same manner as the first
layer, due to incorporation of emulsifier in the second layer as described above.
[0045] In an embodiment, the second layer, in particular the wax, and the third layer build an emulsion. The emulsion
of the second layer and third layer results in a merger and/or fusion of the layers in one unique layer. In other words:
The second layer, in particular the wax, and the third layer are merged into one unique layer. This makes it possible to
45 simplify the assembly of the multilayer. The embodiment, may also allow for a sealing of the unique layer directly to the
first layer.
[0046] The invention also relates to a layered structure comprising a paper base layer and a multilayer as described
above.
[0047] The multilayer can be a coating. The multilayer can be coated on/applied to the surface of the paper base layer.
50 In other words: the layered structure is a system with at least two parts, namely the paper base as a first part and the
multilayer as a second part. The first and second part can have essentially the same areal size. The layered structure
can be regarded as a laminate of the parts and builds a layering, which might also be called a laminate.
[0048] The paper base layer can be paper, fibre substrate or paperboard. Paper may especially be a non-woven
material, pulp-based material. A pulp-based material is a material made from pulp, i.e., from fibers suspended in a liquid
55 (especially water), which is removed at least partially for the production. The fibers may include vegetable fibers (especially
fibers of cellulose (wood-based or from fiber crops)), especially at least 50% or at least 80% vegetable fibers or 100%
vegetable fibers. In addition or as an alternative, the fibers may include mineral fibers or other natural fibers, or man-
made fibers, for example on a calcium carbonate basis.

5
 EP 4 368 665 A1

[0049] In embodiments, the crosslinked polymer composition of the first layer might provide excellent lamination
properties and sealability to the paper base layer and/or to itself.
[0050] In embodiments, at least one of the multilayer and the layered structure is at least one of bio-degradable and
compostable, in particular home compostable. This allows for a good recyclability of the multilayer and/or the layered
5 structure.
[0051] In an embodiment, the first layer is arranged on one flat side of the paper base layer. The paper base layer
comprises two flat sides, like a regular piece of paper. In embodiments, the surface of at least one flat side of the paper
base layer is arranged adjacent to the first layer and/or the third layer. In embodiments, one flat side of the paper base
layer is free of a first layer. In embodiments, the surface of both flat sides of the paper base layer are arranged adjacent
10 to a first layer of the multilayer.
[0052] In embodiments, the first sublayer can be arranged facing the paper base layer and the second sublayer faces
away from the flat side of the paper base layer. In embodiments, the second sublayer can be arranged facing the paper
base layer and the first sublayer faces away from the flat side of the paper base layer.
[0053] In an embodiment, the layered structure provides an adhesion between the paper base layer and the multilayer,
15 in particular the first layer and/or third layer, with sufficient peel strength.
[0054] Another aspect of the invention is a method for producing a layered structure in particular as described above.
The method comprising the steps of:

- providing a paper base layer;

20 - applying a multilayer on the paper base layer, in particular the multilayer as described above.

[0055] In an embodiment, the multilayer is applied to the paper base layer as a foil like element. In embodiments, the
first layer and/or third layer is applied to the paper base layer as a foil like element. Accordingly, the multilayer as a whole
or the first layer and/or third layer can be applied on the paper base layer at low temperature. The multilayer as a whole
25 or the first layer and/or third layer can be in a solid state when applied to the paper base layer. This differs from an
impregnation of the paper base layer with the components of the multilayer as a whole or the first layer and/or third layer
at least by the application temperature. This enables to work at lower temperatures and can reduce the risk of deterioration
of the layered structure.
[0056] Another aspect of the invention is a method for producing a multilayer as described above. The first layer is
30 hydrophilic, and the second layer, comprising a wax, is coated onto the hydrophilic surface of the first layer. The coating
can be realised by precipitating the wax from a heated, alcoholic solution loaded with emulsifier. The alcoholic solvent
can comprise isopropyl alcohol.
[0057] In embodiments, the wax can be emulsified in solution comprising water and an emulsifier.
[0058] In embodiments, the wax can be emulsified in a solution comprising the water-soluble polymer, in particular of
35 the third layer. This may simplify the production of the multilayer by reducing the number of layers.
[0059] Yet another aspect of the invention is a use of at least one of a multilayer, a polymer composition and a layered
structure as described above for packaging, in particular for food packaging, in particular for packaging coffee.
[0060] One aspect of the invention is a packaging comprising at least one of the multilayer, the polymer composition
and/or the layered structure as described above.
40 [0061] In embodiments, the packaging is suited for packaging food products, in particular coffee. The packaging might
be a flexible, pliant packaging material.
[0062] In an embodiment, the paper base layer of the layered structure can be directed to/arranged on the outside of
the packaging. In this case the customer can have the haptic experience of a paper packaging with the improved
properties being inherent to the layered structure as features of the multilayer being arranged inside the packaging.
45 [0063] In embodiments, the packaging, layered structure, polymer composition and/or multilayer meets all requirements
to package highly barrier-sensitive goods, such as coffee, while retaining full recyclability of the paper base layer (also
called earlier material). Due to the water-solubility and excellent biodegradability of the components employed, risks of
pollution and micro-plastics are eliminated completely, thus providing a unique solution for sustainable food-packaging,
without limitations in performance and application-profiles.
50 [0064] In an embodiment, the third layer enables a sealing function to the multilayer, the packaging and/or the layered
structure.
[0065] The unique packaging, layered structure, polymer composition and/or multilayer can be based on non-toxic/food-
safe, biodegradable and/or compostable materials. The packaging, layered structure, polymer composition and/or mul-
tilayer can enable full recyclability of all paper base materials, by usage of water-soluble polymers and additives, while
55 simultaneously providing excellent barrier function against water vapor transmission, oxygen transmission, oil and/or
grease.
[0066] Furthermore, all necessary requirements to processing relevant material-properties, as well as application-
specific material-properties for the undisruptive employment of such packaging, layered structure, polymer composition

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 EP 4 368 665 A1

and/or multilayer in existing production environments are met.

[0067] The water-soluble polymer can comprise a polymer that has a plurality of vinyl alcohol [CH2CH(OH)] groups
in the polymer chain, in particular wherein the water-soluble polymer is poly(vinyl alcohol) (PVOH).
[0068] The water-soluble polymer can be at least one of:
5
- poly(vinyl alcohol) (PVOH),
- cellulose-ether polymer,
- Butenediol-Vinylalcohol-Copolymer (BVOH), and
- Ethyl ene-Vinylalcohol-Copolymers (EVOH).
10
[0069] The water-soluble polymer can comprise at least one vinyl-alcohol copolymer and/or a mixture and/or blend of
two or more vinyl-alcohol copolymers. The copolymers can differ in molar mass, molecular architecture, e. g. branching,
comonomer type and amount, to name only a few variation parameters.
[0070] The water-soluble polymer can comprise further polar comonomers. Examples include maleic acid and maleic
15 acid anhydride, fumaric acid and itaconic acid.
[0071] The PVOH can be a vinyl alcohol rich copolymer and/or vinyl alcohol homopolymer. The water-soluble polymer,
in particular the polyvinyl alcohol (PVOH), can have a degree of hydrolysis of 70% to 99,9%. The degree of saponification
can control the performance to the oxygen transmission barrier. A higher saponification may for instance improve the
oxygen transmission barrier performance. A vinyl-alcohol containing polymer can comprise >75%, in particular >90%,
20 monomer units carrying an OH unit.
[0072] The first layer and/or third layer can comprise at least one of the following polymers:

- Poly(vinyl alcohol) obtained e.g. by the saponification of Poly(vinyl ester) homopolymers or copolymers,
- Ethyl ene-Vinylalcohol-Copolymers (EVOH),
25 - Butenediol-Vinylalcohol-Copolymer (BVOH),

to name only a few.

[0073] In embodiment, the packaging, layered structure, polymer composition and/or multilayer is non-toxic to human,
in particular the packaging, layered structure, polymer composition and/or multilayer is recognized as being safe in food
30 industry, also called food-safe.
[0074] Further preferred embodiments are evident from the dependent patent claims. Features of the method claims
may be combined with features of the device claims and vice versa.
[0075] While the invention has been described in present preferred embodiments of the invention, it is distinctly
understood that the invention is not limited thereto, but may be otherwise variously embodied and practised within the
35 scope of the claims.
[0076] A polymer composition 55 comprising a water-soluble polymer and Polycaprolactone (PCL) 16 is inter- and/or
intramolecular crosslinked by a natural and/or food-safe compound. The natural and/or food-safe compound can be
citric acid. The polymer composition 55 is a food contact material and can be bio-degradable and compostable.
[0077] The water-soluble polymer 18 comprises Poly(vinyl alcohol) (PVOH).
40 [0078] The crosslinked polymer composition 55 can be water-soluble and can act an oxygen barrier. The oxygen
barrier can be characterized in terms of the oxygen transmission rat a material provides.
[0079] A multilayer 5 comprise a first layer 1 with an oxygen transmission barrier, and a second layer 2 with a water
vapor and/or humidity barrier. The first layer 1 comprises a water-soluble polymer and the second layer 2 comprises a
wax 20. The wax 20 can be at least one of a natural wax 20, food-safe wax 20, bio-degradable wax 20, beeswax 20.
45 [0080] The first layer 1 comprises the polymer composition 55 with the crosslinked polymer composition 55 comprising
poly vinyl alcohol (PVOH) and polycaprolactone (PCL).
[0081] The second layer 2 with the wax 20 additionally comprises an emulsifier 21, in order to provide a compatibility
between the hydrophilic first layer 1 and the wax of the second layer 2. The emulsifier 21 can be mono- and diglyceride
of fatty acids, also known as E471.
50 [0082] The second layer 2 is coated onto the hydrophilic surface of the first layer 1 by precipitating the wax 20 from
a heated, alcoholic solution loaded with emulsifier 21. The second layer 2 builds a wax-based film without islanding or
defects in the film, thus providing excellent water vapor and/or humidity barrier.
[0083] The multilayer has a water vapor and/or humidity barrier of a maximum of 15 g/m2 per day at 25°C and a relative
humidity of 80%, in particular a maximum of 10 g/m2 per day at 25°C and a relative humidity of 80%, in particular 3 g/m2
55 per day at 25°C and a relative humidity of 80%, in particular 2 g/m 2 per day at 25°C and a relative humidity of 80%. The
excellent water vapor and/or humidity barrier are in particular provided by the wax included in the second layer. This
makes the multilayer suitable for packaging barrier-sensitive goods, such as coffee.
[0084] The second layer 2 can comprise a water-soluble polymer as e.g. poly vinyl alcohol (PVOH).

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 EP 4 368 665 A1

[0085] The multilayer 5, in particular the first layer 1, in particular the polymer composition 55, has an oxygen trans-
mission rate of a maximum of 3 cm3/m2 per day at room temperature (RT, room temperature = 23°C) and a relative
humidity of 50% (rel. H), in particular the oxygen transmission rate can be maximal 1 cm3/m2 per day at room temperature
and a relative humidity of 50%, in particular maximal 0.2 cm3/m2 per day at room temperature (23°C) and a relative
5 humidity of 50%.
[0086] In some examples according to the invention, the multilayer 5 further comprises a third layer 3. The third layer
3 comprises similar to the first layer 1 a water-soluble polymer to be poly vinyl alcohol (PVOH). The third layer 3 is
applied adjacent to the second layer 2. The second layer 2 is arranged between the first layer 1 and the third layer 3.
The third layer 3 acts as a aroma-barrier for the wax-based second layer 2. The third layer 3 can also act as a sealing
10 promoter.
[0087] The layers of the multilayer 5 can be separable from each other. This allows for an individual recycling of the
layers of the multilayer 5. The layers of the multilayer 5 can be separated from each other under the conditions of the
recycling process. In particular the layer are separable at a maximum temperature of 40 °C, in particular of 38°C to the
most, in particular of 35°C to the most, in particular of 30°C to the most, in an aqueous environment.
15 [0088] In an example the first layer 1 comprises a first sublayer 11 and a second sublayer 12. The second sublayer
12 can be arranged adjacent to the second layer 2.
[0089] The second sublayer 12 can comprise the polymer composition 55 with the crosslinked mixture of PVOH and
Polycaprolactone (PCL) 16. The second sublayer 12 acts as a gas barrier, in particular in relation to oxygen.
[0090] In an example, the multilayer 5 is applied to a paper base layer 51 to build a layered structure 50.
20 [0091] The paper base layer 51 can be paper, fibre substrate or paperboard. Paper may especially be a non-woven
material, pulp-based material. A pulp-based material is a material made from pulp, i.e., from fibers suspended in a liquid
(especially water), which is removed at least partially for the production. The fibers may include vegetable fibers (especially
fibers of cellulose (wood-based or from fiber crops)), especially at least 50% or at least 80% vegetable fibers or 100%
vegetable fibers. In addition or as an alternative, the fibers may include mineral fibers or other natural fibers, or man-
25 made fibers, for example on a calcium carbonate basis.
[0092] The multilayer 5 and/or the layered structure 50 is used for packing food, in particular for packing coffee. The
corresponding packaging comprises the multilayer 5 and/or the layered structure 50 with the paper base layer 51.
[0093] The layered structure 50 can be represented as in the following examples:

30 Example 1

[0094]

component weight composition

35
paper base layer 51 > 50% in wt of the total layered
structure 50
first sublayer 11 of the first layer 1 comprising PVOH 15-25% in wt of the multilayer 5

40
second sublayer 12 of the first layer first layer 1 comprising the polymer 45-60 % in wt of the multilayer 5
composition 55 with crosslinked PVOH a PCL
second layer 2 <1,6% in wt of the multilayer 5
third layer 3 25-35 % in wt of the multilayer 5
45
Example 2

[0095]

50
component weight composition
paper base layer 51 > 50% in wt of the total layered
structure 50
first sublayer 11 of the first layer 1 15-25% in wt of the multilayer 5
55
second sublayer 12 of the first layer first layer 1 comprising the polymer 25-35 % in wt of the multilayer 5
composition 55 with crosslinked PVOH a PCL

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 EP 4 368 665 A1

(continued)

component weight composition

additional layer comprising a polyester derived from caprolactone monomere 15-25% in wt of the multilayer 5
5
second layer 2 <1,6% in wt of the multilayer 5
third layer 3 comprising PVOH 25-35 % in wt of the multilayer 5

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[0096] In a further example 3, the first sublayer 11 of the first layer 1 comprises 75 wt% of PVOH and 22 wt% of PEG
(Polyethylene glycol) and 3 wt % Calcium carbonate and 1 wt% additive (as eg. Silica). The second sublayer 12 of the
first layer 1 comprises 64 wt% of PVOH and 8 wt% of Glycerol and 4 wt % Calcium carbonate and 12 wt% additive (eg.
cellulose) and 11 % additive (e.g. Bentonite). The second layer 2 comprises 50 wt% beeswax and 46 % isopropyl alcohol
and 4 % additive (e.g. E471, being a mono-or diglyceride fatty acid). The third layer 3 is comprises PVOH.
15
[0097] The multilayer 5, the layered structure 50 and/or the packaging comprising the layered structure 50 can be at
least one of bio-degradable and compostable, in particular home compostable.

Claims
20
1. Polymer composition 55 comprising a crosslinked mixture of at least

- a water-soluble polymer and

- Polycaprolactone (PCL) (16).
25
2. The polymer composition (55) according to any of the previous claims, wherein the polymer composition (55) is a
food contact material.

3. The polymer composition (55) according to any of the previous claims, wherein the polymer composition (55) is at
30
least one of bio-degradable and compostable, in particular home compostable.

4. The polymer composition (55) according to any one of claims 1-3, wherein the at least one of the following conditions
is fulfilled:

35
- the water-soluble polymer is at least one of poly(vinyl alcohol) (PVOH), cellulose-ether polymer, Butenediol-
Vinylalcohol-Copolymer (BVOH), and Ethylene-Vinylalcohol-Copolymers (EVOH);
- the water-soluble polymer is inter- and/or intramolecular crosslinked by a natural and/or food-safe compound.

5. The polymer composition (55) according to any one of claims 1-4, wherein the water-soluble polymer is PVOH and
40
is inter- and/or intramolecular crosslinked by citric acid with the Polycaprolactone (16).

6. Multilayer (5) comprising:

- at least one first layer (1) comprising a polymer composition 55 according to one of the claims 1-5;
45
wherein the first layer (1) has an oxygen transmission barrier, and
- at least one second layer (2),
wherein second layer (2) has a water vapor and/or humidity barrier;

wherein the second layer (2) comprises a wax (20), in particular a natural wax, in particular food-safe wax, in particular
50
bio-degradable wax, in particular bee wax.

7. The multilayer (5) according to any of the previous claims, wherein the multilayer (5) has a water vapor and/or
humidity barrier of a maximum of 15 g/m2 per day at 25°C and a relative humidity of 80%, in particular a maximum
of 10 g/m2 per day at 25°C and a relative humidity of 80%, in particular 3 g/m2 per day at 25°C and a relative humidity
55
of 80%, in particular 2 g/m2 per day at 25°C and a relative humidity of 80%.

8. The multilayer (5) according to any of the previous claims, wherein the multilayer (5) is at least one of bio-degradable
and compostable, in particular home compostable.

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 EP 4 368 665 A1

9. The multilayer (5) according to any of the previous claims, wherein the multilayer (5) comprises a third layer (3),
wherein the third layer (3) is arranged adjacent to the second layer (2).

10. The multilayer (5) according to any of the previous claims, wherein the second layer, in particular the wax, and the
5 third layer are merged into one unique layer.

11. Layered structure (50) comprising:

- a paper base layer (51) and

10 - a multilayer (5) according to any of the previous claims 6-9.

12. Method for producing a layered structure (50), in particular a layered structure (50) according to claim 11, comprising
the steps of:

15 - providing a paper base layer (51);

- applying a multilayer (5) according to one of claims 6-10 on the paper base layer (51).

13. Method for producing a multilayer (5) according to one of the previous claims 6-10,

20 wherein the first layer (1) is hydrophilic, and

wherein the second layer (2) is coated onto the hydrophilic surface of the first layer (1) by precipitating the wax
(20) from a heated, alcoholic solution loaded with emulsifier (21).

14. Use of at least one of a multilayer (5) according to any one of claims 6-10, a polymer composition (55) according
25 any one of claims 1-5 and a layered structure (50) according to claim 10 for packing, in particular for food packing,
in particular for packing coffee.

15. Packaging comprising at least one of a multilayer (5) according to any one of claims 6-10, a polymer composition
(55) according any one of claims 1-5 and a layered structure (50) according to claim 11.
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REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 22171579 [0003] • EP 22171641 A [0003]

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