WO2024068412A1 - Plastique de marquage pour recyclage - Google Patents

Plastique de marquage pour recyclage Download PDF

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Publication number
WO2024068412A1
WO2024068412A1 PCT/EP2023/076017 EP2023076017W WO2024068412A1 WO 2024068412 A1 WO2024068412 A1 WO 2024068412A1 EP 2023076017 W EP2023076017 W EP 2023076017W WO 2024068412 A1 WO2024068412 A1 WO 2024068412A1
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WO
WIPO (PCT)
Prior art keywords
packaging material
label
user
plastic
oxide
Prior art date
Application number
PCT/EP2023/076017
Other languages
English (en)
Inventor
Arkadi Maisels
Florian Böhl
Ulrich Boes
Beate KUMMER
Jochen Mößlein
Original Assignee
Evonik Operations Gmbh
Polysecure Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations Gmbh, Polysecure Gmbh filed Critical Evonik Operations Gmbh
Publication of WO2024068412A1 publication Critical patent/WO2024068412A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0203—Separating plastics from plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0279—Optical identification, e.g. cameras or spectroscopy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0282—Specific separating techniques using information associated with the materials, e.g. labels on products

Definitions

  • the present invention relates to plastic packaging material with a labelling system that enables the packaging material to be more efficiently and correctly recycled.
  • the labelling system is at least a double labelling system.
  • the plastic packaging material comprises at least a first label targeting the end-user and the second label targeting an industrial waste sorting machine.
  • Plastic materials are widely used in the packaging industry because of plastic's ability to protect a product from physical damage, loss, and other degradation. Also, plastic material enables the product packaged within to reach the consumer in the same state it was in when packaged at the time of distribution.
  • the currently used labels are mostly printed visible barcodes, and trademarks can be read and optically recognized by the human eye and by detectors in the wate management industry, provided they are placed/held in some defined way.
  • These labels can hardly be recognized by current automated plastic waste sorting equipment due to a combination of reasons, namely: low detection time (milliseconds), random orientation of plastic packaging in detection unit, and high extent of deformation of plastic packaging as they are collected and processed by waste collecting companies. The combination of these three reasons makes the currently used labels simply unreadable, as they become unrecognizable when the packaging material reaches the waste management industry.
  • the present invention attempts to solve the problems above by providing a plastic packaging material that is labelled such that it can be efficiently recycled.
  • the material comprises at least two different labels, a first and a second label.
  • the first label enables the end-user, namely the human being who used the packaging material to dispose of the material appropriately. More in particular, the enduser throws the packaging material in the appropriate and correct rubbish bin as a result of the first label on or printed on the packaging material.
  • the second label enables the correctly disposed packaging material to be further sorted by the waste management industry accurately. In particular, the second label targets the waste management industry and not the end user and is therefore invisible to the end user.
  • Packaging material with at least two labels according to any aspect of the present invention enables the packaging material to be correctly disposed and subsequently collected and properly recycled thus reducing the amount of waste, particularly plastic waste.
  • plastic packaging material comprising:
  • the second label comprises information on the material origin, type and/or use and wherein the second label is at least one up-conversion based florescent marker that is invisible to the end-user.
  • the packaging material is marked with a first mark (a first label), particularly a visible label to the naked eye, which is clearly distinguishable and easily recognizable by the end-user.
  • the first label may be used uniformly on all packaging material such that all material of the same origin may be disposed in the same manner.
  • all plastic packaging material may comprise or be printed with the same or similar first label such that all the plastic packaging material with the same or similar first label is disposed the same way.
  • the first label being clearly distinguishable and possibly uniform, enables the end-user to make a quick decision on the right disposal (right trash bin) to throw the packaging material away. This improves the quality of waste sorting due to reduction of wrong disposal decisions by the end-user.
  • the correct disposal of packaging material by the end user increases the fraction of packaging materials, particularly plastic packaging material, accessible for recycling. More in particular, the first label enables the end-user to appropriately recycle the packaging material.
  • Examples of the first label according to any aspect of the present invention may be visible and eye-catching symbols and/or words.
  • the first label may be the sign for ‘Grunelitz’ in used in Germany or equivalents found internationally.
  • the distinct types of labels that may be used to target the end-user to throw the packaging material into the right rubbish bin may vary depending on the country where the packaging material is found in. Regardless of different terminology or labels used in different countries to describe different distinct means of disposal of a packaging material, the overall concept of the labelling according to any aspect of the present invention is the same and applicable in any one of these countries.
  • the first label according to any aspect of the present invention may be the sign for ‘Grunelitz’ in used in Germany or equivalents found internationally.
  • the first label according to any aspect of the present invention may be a sign for recycling, and/or in combination with the word recyclable.
  • the first label according to any aspect of the present invention may comprise word combinations such as “for plastics bin only”, “dispose as plastics waste for proper recycling”, “packaging disposable as plastics waste only for recycling”, “this packaging will be recycled, if disposed as plastics waste” etc.
  • the packaging material according to any aspect of the present invention may comprise only a single first label, not to confuse the end-user.
  • the packaging material may comprise more than one first label when the packaging material is to be used internationally and each country in which the packaging material ends up in has a different label for recyclable material.
  • the term ‘equivalents’ as used herein refers to different terminology or symbols for the same or similar recycling quality of a packaging material that is used in different countries.
  • the packaging materials that can be recycled in UK may be the same as the packaging materials that can be recycled in Germany. However, they may be labelled differently in each of these countries.
  • the same recycling capability of a packaging material may be labelled under a different term in each of these countries.
  • ‘Equivalents’ thus refers to the same or significantly similar first labels that are used different countries for the same packaging material.
  • the same packaging material is further marked with a second mark (a second label), that may not necessarily be visible to the naked eye of the end-user.
  • the second label on the packaging material may be invisible to the end-user, with information at least on material origin and recycling recommendation. More in particular, the second label contains information on the kind of material, material origin, manufacturer, brand owner, purpose of packaging material, etc.
  • This information is stored in for example a digital product passport that is or part of the second label.
  • the information of the digital product passport may be read by at least one industrial waste sorting machine, particularly, the digital product passport may be accessible for high-speed optical analytics systems that are usually installed in automated waste sorting machines.
  • the second label is at least one up- conversion based florescent marker that is invisible to the end-user
  • the second label may be recognised by currently used industrial waste sorting machines where the detection time is low, namely milliseconds.
  • the second label being a fluorescent marking that is continuous and/or invisible for the human eye enables the plastic packaging according to any aspect of the present invention to be recognizable at any orientation and with any deformation.
  • the digital product passport stores all relevant information on the packaging material according to any aspect of the present invention online in a compressed form.
  • This digital product passport is in the form of the second label on the packaging material.
  • the second label may be a QR code that may be read or scanned by the waste sorting machine.
  • information on the packaging material may be accessed by the waste sorting machine which may be stored in a database (product passport register).
  • the use of digital product passport is intended to ensure efficient and accurate recycling of packaging material. Further, the use of the digital product passport also reduces human error by making the process more automatic and digital.
  • the second label according to any aspect of the present invention may be a fluorescent marker, or a one up-conversion based florescent marker.
  • the ‘up-conversion-based florescent marker’ used according to any aspect of the present invention refers to a volume-based marking of the packaging plastic material. That is to say, the plastic packaging material does not comprise visible markers as the second label, but the plastic is in itself manufactured with the second label (i.e. the up-conversion-based florescent marker) integrated in the plastic.
  • the markers used according to any aspect of the present invention is thus part of the plastic material (i.e. the polymer).
  • the plastic according to any aspect of the present invention is thus combined with the up-conversion fluorescent marker during the manufacturing process of the packaging material and/or during the extrusion process of the packaging material.
  • the up-conversion fluorescent marker integrated within the plastic has the advantage that the marker is never lost, and the plastic can almost always be sorted and therefore recycled. Further, regardless of the plastic packaging material being distorted/ deformed or regardless of the orientation of the plastic material in the sorting machine, the integrated up-conversion fluorescent marker in the packaging material can successfully be sorted and therefore recycled.
  • the currently available packaging plastic materials may have labels attached to them instead, if anything at all, and these may fall off before reaching the sorting machine and cannot thus be detected and sorted and therefore cannot be recycled. Further, since the marker is a property of the plastic material in the packaging material according to any aspect of the present invention, there is a higher chance of the plastic material being almost always sorted even when the sorting is fast.
  • the up-conversion fluorescent markers according to any aspect of the present invention can be added to the plastics directly or via masterbatch route.
  • the masterbatch route is clearly preferrable.
  • the up-conversion fluorescent marker concentration in masterbatch can be in range 100 ppm - 500 ppm.
  • the up-conversion fluorescent marker concentration may be about 50-1000, 50-950, 50-900, 50-850, 50-800, 50-750, 50-700, 50-650, 50-600, 50-550, 50-500, 100-1000, 100-950, 100-900, 100-850, 100-800, 100-750, 100-700, 100-650, 100-600, 100-550, 100-500, 150-1000, 150-950, 150-900, 150-850, 150-800, 150-750, 150-700, 150-650, 150-600, 150-550, 150-500, 200-1000, 200-950, 200-900, 200-850, 200-800, 200-750, 200-700, 200-650, 200-600, 200-550, 200-500, 250-1000, 250-950, 250-900, 250-850, 250-800, 250-750, 250-700, 250-650, 250-600, 250-550, 250-500, 300-1000, 300-950, 300-900, 300-850, 250-800, 250-750
  • the up-conversion fluorescent marker concentration may be about 50, 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, or 1000 ppm in the masterbatch.
  • the masterbatch with 500 ppm of up-conversion fluorescent marker material can be manufactured through mixing of 50 kg of the granulated plastic material with 10 g of up-conversion fluorescent marker material and 20 ml of dispersion additive in a tumble mixer. This masterbatch can then be diluted through addition of non-marked plastics granulate in extruder.
  • the final concentration of up-conversion fluorescent marker in plastics may be in the range 1 ppm - 200 ppm.
  • the final concentration of up-conversion fluorescent marker in the food-contact plastic may be 1-200, 1-150, 1-100, 1-50, 1-45, 1-40, 1-35, 1-30, 1-25, 1-20, 1-15, 1-10, 1-5, 5-200, 5- 150, 5-100, 5-50, 5-45, 5-40, 5-35, 5-30, 5-25, 5-20, 5-15, 5-10, 10-200, 10-150, 10-100, 10-50, 10-45, 10-40, 10-35, 10-30, 10-25, 10-20, 10-15, 15-200, 15-150, 15-100, 15-50, 15-45, 15-40, 15-35, 15-30, 15-25, 15-20, 20-200, 20-150, 20-100, 20-50, 25-200, 25-150, 25-100, 25-50, 30-200, 30-150, 30-100, 30-50, 40-200, 40-150, 40-100, 50-200
  • the final concentration of up- conversion fluorescent marker in the food-contact plastic may be about 1 , 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 125, 150, 175, or 200 ppm. Even more in particular, the final concentration of up-conversion fluorescent marker in the plastic packaging material according to any aspect of the present invention may be about 10 ppm.
  • the homogenization of the plastics-marker mixture i.e. plastic material with the up- conversion fluorescent marker
  • plastics-marker mixture i.e. plastic material with the up- conversion fluorescent marker
  • the improvement of the homogeneity of the marker distribution on the masterbatch can be achieved by use of dispersion additives, for example TEGOMER®, TEGOPREN®, TEGODISPERS®, Epolene®.
  • fluorescent refers a luminescence phenomenon in which electron de-excitation occurs almost spontaneously, and in which emission from a luminescent substance ceases when the exciting source is removed. In fluorescent materials, the excited state has the same spin as the ground state. A compound capable of fluorescence is termed a “fluor”.
  • luminescence refers to the process in which light is emitted from a material at a different wavelength than that which is absorbed. It is an umbrella term covering both fluorescence and phosphorescence.
  • the term “up-conversion” refers to a process where light can be emitted with photon energies higher than those of the light generating the excitation.
  • Photoexcitation at a certain wavelength in the near infrared (NIR) followed by luminescence at a shorter wavelength in the VIS is called NIR to VIS photon up- conversion.
  • This phenomenon may be considered to be rather unusual as low energy photons are “converted” to higher energy photons.
  • At least two NIR photons are required to generate one VIS photon.
  • fluorescence is emitted by a medium as a consequence of being excited with incident light, the wavelength of the fluorescence is usually longer than that of the exciting light. Photon energy is thus reduced.
  • Up- conversion fluorescence may also occur in some cases where the wavelength of the emitted light is shorter.
  • a more elaborate disclosure of the mechanism behind up- conversion markers is provided in EP2297678 B1. Further, photo-luminescent properties of rare earth compounds are described in US7, 184,203 which may also be used according to any aspect of the present invention.
  • Suitable lanthanide ions are the rare earths selected from cerium (Ce), erbium (Er), europium (Eu), dysprosium (Dy), gadolinium (Gd), holmium (Ho), lanthanum (La), lutetium (Lu), neodymium (Nd), praseodymium (Pr), promethium (Pm), samarium (Sm), terbium (Tb), thulium (Tm), and ytterbium (Yb).
  • lanthanide ions such as ytterbium (Yb3+), holmium (Ho3+), Erbium (Er3+) or Thulium (Tm3+), or Yb3+/Er3+ co-dopants may be used.
  • Hexagonal sodium yttrium fluoride, NaYF4 may be specifically used for green (Yb3+/Er3+ doped) and blue (Yb3+/Tm3+ doped) up-conversion phosphors.
  • Blue light can also be alternatively generated by Yb,Tm:YLF (yttrium lithium fluoride) when pumped with diode laser light having a wavelength of approximately 958 to approximately 959 nm
  • green visible light can be efficiently generated by Yb,Er:NYF (sodium yttrium fluoride) when pumped with diode laser light having a wavelength of approximately 976 nm
  • red visible light can be efficiently generated by Yb,Er:KYF(potassium yttrium fluoride) or Yb,Er:YF3 when pumped with diode laser light having a wavelength of approximately 973.5 nm to approximately 976 nm.
  • US6,897,999 discloses different up-conversion markers that
  • the up-conversion fluorescent marker may be an oxide and/or salt of rare- earth metals. More in particular, the up-conversion fluorescent marker may be selected from the group consisting of yttrium oxide, yttrium ytterbium oxide, yttrium ytterbium oxysulfide, titanium dioxide, cobalt oxide, lanthanum oxide, europium oxide, coordination complexes of rare-earth metals and mixtures thereof.
  • end-user refers to the final user of the packaging material and/or the user of the packaging material that finally disposes of the packaging material into the rubbish bin.
  • the end-user is thus the human being, or consumer that disposes of the packaging material.
  • packaging material refers to material that is particularly used for packaging items.
  • Packaging material may be of any origin that may be used to wrap and/or seal any item that needs to be packed.
  • packaging material refers to any material, container or wrapping, used for or in connection with the transport, handling, protection, marketing or sale of any supplies, that would particularly be used by the end-user.
  • Packaging material may also include any material, container or wrapping used for the containment of the supplies.
  • packaging material does not include the supplies in itself.
  • Packaging materials are intended to enclose or hold together the materials that are to be packed. In other words, the material that is to be packed can be packed into or onto the packaging material.
  • the packaging material can be a load carrier.
  • the most important packaging materials include crates, boxes, containers, wire baskets, pallets and the like.
  • the packaging material may be plastic material. More in particular, the plastic material may be selected from the group consisting of Polyethylene (PE), High-Density Polyethylene (HDPE), Low-Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Polyvinylchloride (PVC), Polypropylene (PP), Polystyrene (PS), polyamide (PA), polyethylene-terephthalate (PET), Polyethylene terephthalate glycol (PETG) polymethylmethacrylate (PMMA), polycarbonate (PC), expanded polystyrene (EPS), extruded polystyrene (XPS), expanded polypropylene (EPP), polyurethanes (PU), polyvinylchloride (PVC), glass-fiber reinforced PP, epoxy-based composites, multilayersystems of above-mentioned materials and mixtures thereof.
  • Packaging material may also include flexible packages made from films or thin sheets of polyolefins or plasticized PVC.
  • the first and second labels according to any aspect of the present invention may be in the form of continuously printed mark on the surface of the packaging material.
  • the printing ink of the first and/or second labels may be removable in industrial waste washing equipment.
  • the printing ink can contain markers and/or tracers. These markers can be fluorescent markers, which are recognizable by means of optical analytic equipment in waste sorting units.
  • the use of different fluorescent markers with different fluorescence spectrums may enable a legend to be created wherein each fluorescent colour codes for a unique identifier that is related to the packaging material. For example, each fluorescent colour codes for a different quality of the packaging material, such as the packaging type, packaging material, packaging manufacturer, and brand behind the packed product etc.
  • the different fluorescent colours may then be used as second label on the packaging material according to any aspect of the present invention such that the waste sorting machine can correctly sort the packaging material for recycling purposes.
  • the first and/or second label may be made from deinkable ink.
  • the first and/or second labels may be printed on the surface of the packaging material by deinkable ink.
  • the deinkable ink is selected from the group consisting of UV-curable resins, acrylic resins, methacrylic resins, polyurethane resins, ethoxy resins and mixtures thereof.
  • the deinkable ink may deink at a temperature of 50°C or below or 45, 40, 35, 30°C or below. Even more in particular, the deinkable ink may be UV-curable MMA-based ink.
  • a method of separating recyclable plastic packaging material from a mixture of recyclable plastic and non-recyclable plastic comprising: contacting the mixture to at least one waste sorting machine, wherein the recyclable plastic is the plastic packaging material according to any aspect of the present invention.
  • the waste sorting machine is a high-speed industrial sorting machine with a high-speed optical analytics system.
  • the high-speed industrial sorting machine may be capable of infra-red adsorbing markerbased sorting.
  • the combination with near infra-red analytics marker-based sorting will allow the separation of plastics waste into groups according to its application and according to its chemical composition, creating, in this way, waste streams for high- value recyclates.
  • Examples of infra-red analytics marker-based sorting include a standard infrared sorting machine additionally equipped with marker-specific sensors, or with updated detection software, which includes marker emission spectrum in detection algorithm.
  • the high-speed industrial sorting machine according to any aspect of the present invention may have a conveyer band speed of 2 m/s or more. In particular, 2, 2.5, 3, 3.5, 4, 4.5, 5 m/s or more. Even more in particular, the conveyer band speed may be between 2 m/s and 5 m/s.
  • a double labelling system for marking plastic packaging material to be recycled, the double labelling system comprising: a first label readable by an end-user, wherein the first label is visible to the enduser and distinct for packaging material that is recyclable; and a second label readable by at least one industrial waste sorting machine, wherein the second label comprises information on the material origin, type and/or use and wherein the second label is at least one up-conversion based florescent marker that is invisible to the end-user.
  • plastic packaging material is selected from the group consisting of Polyethylene (PE), High-Density Polyethylene (HDPE), Low-Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Polyvinylchloride (PVC), Polypropylene (PP), Polystyrene (PS), polyamide (PA), polyethylene-terephthalate (PET), Polyethylene terephthalate glycol (PETG) polymethylmethacrylate (PMMA), polycarbonate (PC), expanded polystyrene (EPS), extruded polystyrene (XPS), expanded polypropylene (EPP), polyurethanes (PU), polyvinylchloride (PVC) and mixtures thereof.
  • PE Polyethylene
  • HDPE High-Density Polyethylene
  • LDPE Low-Density Polyethylene
  • LLDPE Linear Low Density Polyethylene
  • PVC Polyvinylchloride
  • PVC Polypropylene
  • PP Polystyrene
  • the second label is an up-conversion based florescent marker.
  • the first and/or second label is made from deinkable ink.
  • the first layer is a deinkable colorless primer
  • the second layer contains printed signs of “Der Grunelitz”
  • the composition of primer corresponds to the Example 1 from WO 2021/165081
  • This primer was diluted with ethanol to a suitable viscosity (see Example 4 from WO 2021/165081) and applied on the surface of polypropylene film as a primer. On the top of this surface were printed signs of “Der Gruneillon” by conventional printing inks and cured, the distance between signs was 10 cm.

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  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un matériau d'emballage en plastique, le matériau comprenant : une première étiquette lisible par un utilisateur final, la première étiquette étant visible pour l'utilisateur final et distincte pour le matériau d'emballage qui est recyclable ; et une seconde étiquette lisible par au moins une machine de tri de déchets industriels, la seconde étiquette comprenant des informations sur l'origine, le type et/ou l'utilisation du matériau, et la seconde étiquette étant au moins un marqueur fluorescent basé sur une conversion ascendante qui est invisible pour l'utilisateur final.
PCT/EP2023/076017 2022-09-30 2023-09-21 Plastique de marquage pour recyclage WO2024068412A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP22198940 2022-09-30
EP22198940.3 2022-09-30

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WO2024068412A1 true WO2024068412A1 (fr) 2024-04-04

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