Enzyme-resin composition, toner printing process, method for enzyme-resin composition formation and modification

Abstract

The present invention relates to a composition comprising an electrostatically chargeable resin particle and a polymer-modifying enzyme capable of catalytically depolymerizing the resin particle into monomers and / or oligomers upon bringing the composition into contact with water, preferably at a water temperature Tw wherein the enzyme is catalytically active but below the glass transition temperature of the composition. It further relates to a method for producing said compositions, and a method for modifying said resin particle by bringing the resin particle in contact with water, preferably at a water temperature Tw wherein the enzyme is catalytically active but below the glass transition temperature of the composition.

Description

[0001] Enzyme-resin composition, toner printing process, method for enzyme-resin composition formation and modification

[0002] Field of Invention

[0003] The field of the invention relates to a composition comprising an electrostatically chargeable resin particle and an enzyme. It relates to a composition comprising an electrostatically chargeable resin particle and a polymer-modifying enzyme capable of catalytically depolymerizing the resin particle into monomers and / or oligomers upon bringing the composition into contact with water, preferably at a water temperature Tw wherein the enzyme is catalytically active but below the glass transition temperature of the composition. It further relates to a method for producing said compositions, and a method for modifying said resin particle by bringing the resin particle in contact with water, preferably at a water temperature Tw wherein the enzyme is catalytically active but below the glass transition temperature of the composition.

[0004] Microplastics are found to be accumulating into the environment, creating negative effects both for humans as for other living organisms in the world. It is therefore of the utmost importance to limit its presence in all consumer products and avoid the release into the environment. Additionally, consumer products containing microplastics need to be labeled as such. The consumer generally sees any kind of hazardous labeling as a negative trait of a product, and it is therefore desirable to limit the amount of labels on products. Furthermore, the public opinion is getting more critical every day and critics the growing use of plastics because of the negative impact they have on the carbon footprint and the use of fossil sources. Even polymeric systems based on sustainable building blocks or making use of recycled materials still pose some environmental issues when released into the nature.

[0005] It is therefore desirable that whenever microplastics are present, their potential harm to the environment is limited as much as possible.

[0006] Electrostatically chargeable resin particles, such as a toner or a powder coating, generally comprises polymers that would be considered microplastics. Whenever such particles would be spilled, they could pose harm to their environment.

[0007] There is thus a need for electrostatically chargeable resin particles that are less harmful to the environment. Currently, no solutions to this problem exist, if one wants to continue to work with electrostatically chargeable resin particles, such as a toner or a powder coating. Alternatives for printing exist in e.g. inkjet. However, inkjet has many drawbacks compared to electrophotographic (EP) solutions. Inkjet is also based on microplastics (polymeric emulsions of polymer encapsulated pigment particles), it often contains many other harmful chemicals, such as volatile organic compounds (VOCs) which are equally harmful to the environment as microplastics, if not even more harmful in a different way, for example by increasing the greenhouse effect. Additionally, inkjet is much more limited in substrate if acceptable color saturation and adhesion is required. Furthermore, quality-wise EP solutions give better image quality results than inkjet printing. Lastly, inkjet inks also comprise a plethora of microplastics. It is thus not satisfactory to switch from inkjet to EP in order to overcome the problem of microplastics.

[0008] The same reasoning applies to liquid toner.

[0009] An additional problem with electrostatically chargeable resin particles, such as a toner or a powder coating, is the recyclability of both the particles as the packaging material. Particles can get stuck on the inside of its packaging material, e.g. a toner bottle. Sucking the particles from the toner bottle does not always clean the bottle well enough to recycle the bottle correctly, as some toner dust will be mixed in during the recycling process. To clean the bottle more thoroughly, water or another solvent could be added to dissolve the leftover toner. However, the waste water containing the toner will need to be collected separately as this will contain microplastics. This waste water can be further purified or filtered, but this is an expensive and time-consuming process, and is thus not always desirable. of the invention

[0010] It is an object of the invention to provide electrostatically chargeable resin particles that are capable of losing their microplastic character when entering into an environment containing water, while still being functional e.g. as toner or a powder coating. The microplastic character of the resin particles can be lost by depolymerization and / or becoming (more) water soluble.

[0011] It is further an object of the invention that in the case of the electrostatically chargeable resin particles being toner particles, the printing results of prints with said toner are still acceptable.

[0012] It is further an object of the invention to provide methods for producing said electrostatically chargeable resin particles, and using said particles in a printing process. It is also an object of the invention to provide methods for depolymerizing and / or increasing the water solubility of the composition, such that the composition is no longer considered to be a microplastic.

[0013] It is further an object of the invention to provide methods for deinking a printed substrate.

[0014] There is thereto provided a composition comprising a resin particle with a diameter between 5 and 120 micrometer and an enzyme, wherein the particle is electrostatically chargeable and wherein the enzyme is attached to a surface of the particle. The enzyme is a polymer-modifying enzyme capable of either :

[0015] -catalytically depolymerizing the resin particle into monomers and / or oligomers. In particular upon bringing the composition into contact with water at a water temperature Tw at which the enzyme is capable of depolymerizing the resin particle into monomers and / or oligomers.

[0016] - catalytically modifying the resin particle such that the water solubility of the resin particle increases.

[0017] There is thereto also provided a toner or a powder coating composition, in particular for printing, more in particular a dry toner or a dry powder coating for printing, such as laser printing. The toner or powder coating composition comprises:

[0018] - an electrostatically chargeable polymeric resin particle; wherein the resin particle is a toner particle or a powder coating, preferably a toner particle, most preferably a dry toner particle, wherein the resin particle preferably has a volume average particle diameter between 5 and 120 micrometer, as measured with a coulter counter; and

[0019] - an enzyme, wherein the enzyme is a polymer-modifying enzyme for depolymerizing and / or increasing the water solubility of the polymeric resin particle; wherein the enzyme is attached to a surface of the resin particle.

[0020] It has been found by the inventors that by attaching a polymer-modifying enzyme to an electrostatically chargeable resin, the enzyme did not lose its enzymatic activity. The resin could thus, surprisingly, upon bringing the composition into contact with water at a suitable temperature, be either catalytically broken down by the enzyme to monomers and oligomers, and / or be modified such that the water solubility of the resin particle was increased. Moreover, the resin did not lose its electrostatically chargeability, imaging, coloring, adhesion and fusing properties.

[0021] In this manner, a desired printing behavior and printing results could be maintained and / or achieved. It has further been found that particles having a volume average particle diameter between 5 and 120 micrometer (pm), preferably 5 to 30 micrometer, could achieve improved print quality, finer detail, and more efficient and / or safe use of toner. Moreover, it was also found that particles which are sized between 5 and 120 micrometer (pm), preferably 5 to 30 micrometer, could be catalytically broken in an improved manner, believably because of an easier access to modify the particle and / or access to increase the water solubility of the resin particle. Moreover, advantageously, the range between 5 and 120 micrometer (pm), preferably 5 to 30 micrometer allows for improved chargeability, imaging, coloring, adhesion and fusing properties.

[0022] It has further been found that it is necessary that the enzymes are attached to the resin for an optimal result.

[0023] If the composition would be dropped in a larger body of water, it is possible that the enzymes would drift off from the resins if the enzymes are not attached to the resin, and the enzymes would thus not be able to catalytically modify the resins. In smaller volumes of water, the enzymes were catalytically active independent of whether the enzymes were or were not attached to the resin. Additionally, in case the resin is a dry toner, printing results were found to be less satisfying when enzymes were added without attaching them to the resin surface: the enzymes were visible as white spots in the printed image. When the enzymes are finely mulched, the white spots become less apparent. However, this would thus require an extra, energy-intensive step. Thus by attaching the enzyme to the resin surface, the resin can be broken down even in a larger body of water, while still be functional as e.g. toner.

[0024] Lastly, if the enzyme would not be attached to the toner resin, the enzyme would not be transferred together with the toner during the printing or image formation process. Therefore, the enzyme could not be used in a further deinking process. Additionally, the enzyme could be left behind in the printer and might cause defects if the printer is not cleaned sufficiently.

[0025] Preferably, the enzyme is capable of the depolymerizing and / or the modification of the resin particle, upon bringing the composition into contact with water at a water temperature Tw at which the enzyme is capable of modifying the resin particle. Preferably, Tw satisfies the following condition: Tg-D < Tw < Td, wherein Tg, Tw, Td and D are as follows. Tg = glass transition temperature of the composition. Td = denaturation temperature of the enzyme. As used herein, D = 20 °C, preferably 15 °C, more preferably 10 °C, most preferably 5 °C.

[0026] Generally herein, the Tg is preferably measured with Differential Scanning Calorimeter (DSC Q20 from TA Instruments), heating rate 20°C / min, 2 heating cycles, the Tg is then determined in 2ndheating step, by half height of the height in slope of the thermogram. Tw = temperature of the water.

[0027] Generally herein, the denaturation temperature of the enzyme (or Td as referred to herein) is typically the temperature where the activity of the enzyme stops due to chemical deformation or reaction, the Td can be determined based on the conditions of the composition and / or is preferably determined at a pH 8.

[0028] The volume average particle diameter as referred to herein is measured with a Coulter counter.

[0029] In an embodiment, the resin particle is a toner particle or a powder coating, preferably a dry toner particle. In the case wherein the resin is a printing dry toner, the printing results did not deteriorate when printing the toner-enzyme composition, compared to printing without the presence of an enzyme. Alternatively, the resin particle might be a liquid toner particle.

[0030] In an embodiment, the resin particle is a powder coating. In the case wherein the resin is a powder coating, the powder coating capabilities are not significantly influenced by the attachment of an enzyme. Hence, advantageously the powder coating capabilities are maintained, even while enjoying the deinking capacity as a result of the enzyme.

[0031] In an embodiment, the resin particle comprises any of a polyester, polyether, polyolefin, polyurethane, polyester acrylate, polyacrylate and / or styrene-butadiene copolymer, preferably polyester, polyether and / or polyacrylate, most preferably polyester. Any of these resin polymer are useable as electrostatically chargeable polymeric resins, and have the advantage that they can be used as toner particles or as a powder coating.

[0032] In particular, printing with toner particles comprising polyester, polyether and polyacrylates results in better printing results than other polymers. Especially preferred is polyester, as this gives the best printing results. In an embodiment, the polymer-modifying enzyme is capable of catalytically depolymerizing the resin particle into monomers and / or oligomers of a length of two to three monomers, preferably into monomers. The smaller the particles are broken down, the better it will be for the environment as these are less harmful. Additionally, monomers can be separated from the aqueous environment, thus being reused for other applications. In an embodiment, the polymer-modifying enzyme is capable of hydrolyzing the resin particle. An advantage of hydrolyzation is that no additional cofactors are required, such as is the case in a oxidation reaction.

[0033] In an embodiment, the enzyme is chosen from: esterase, protease, hydrolase, lipase, ligase, cutinase, PETase, PET hydrolase, polyurethane esterase, lyases, oxido-reductase, transferase, isomerase, kinase, haloalkane dehalogenase. More preferably the enzyme is chosen from esterase, protease, hydrolase, lipase, ligase, cutinase, PETase, PET hydrolase, polyurethane esterase, lyases, transferase, isomerase, kinase, haloalkane dehalogenase, even more preferably chosen from cutinase, lipase, ligase. Advantageously, these enzymes can act upon the resin particle upon exposure to certain conditions such that the resin can be degraded and will not be harmful to the environment, such as marine life.

[0034] In an embodiment, the mass ratio of the enzyme to the resin particle is between 0.05% and 8.0 %, preferably between 0.1% and 5.0%, more preferably between 0.2% and 2.0 %. It was found that when the mass ratio is higher, the coating / printing results are negatively influenced, as the charging and developing processes of the printer are negatively influenced because of the low mass concentration of the resin particles.

[0035] In embodiments where the toner particles comprise polyester, polyether and polyacrylates, it is preferred that the enzyme is chosen to be of any of the following types: a cutinase, a ligase, a lipase, and a PETase, a peroxidase, an oxidase, a laccase, an oxidoreductase, preferably a lipase, a ligase or cutinase. In this manner, advantageous results could be achieved in view of both printing, print quality and product characteristics such as recyclability properties, degradability, environmental concerns. According to an embodiment, the toner particle comprises a polyester resin and the enzyme is chosen from a hydrolase, a cutinase, a lipase, preferably a lipase.

[0036] On the other hand, when the mass concentration of the enzyme becomes too low in view of the mass concentration of the resin, the catalytic depolymerization speed of the resin is too strongly reduced. In an embodiment, the enzyme is attached to the surface of the particle via van der Waals force and / or Coulomb force. These bonds are bonds strong enough to prevent the enzyme breaking away from the resin particle.

[0037] Generally, preferably, the resin particle is a polyester resin and / or an acrylate resin. Surprisingly, highly desired printing results could be achieved, including one or more of durability, flexibility and adhesion to surfaces, image detail. In an embodiment, the resin particle is formed from a polyester resin. The polyester resin is typically a thermoplastic polymer derived from the polycondensation of a diol component and a dicarboxylic acid component. Advantageously, high thermal stability and excellent adhesion properties could be achieved which is enabling a good image reproduction and durable prints. In an embodiment, the resin particles is formed from an acrylate resin. The acrylate resin is typically derived from the polymerization of acrylate monomers. Advantageously, high gloss, and an efficient energy consumption (lower melting point) could be achieved, in particular during the fusing process during printing.

[0038] Preferably, the enzyme is a lipase and the resin particle is a polyester resin or an acrylate resin, more in particular a polyester resin or a styrene acrylate resin toner. Surprisingly, desired printing results could be achieved while the microplastic character was lost afterwards which is highly beneficial seen from environmental standpoint. The styrene acrylate resins may further improve efficient energy consumption (lower melting point) due to the presence of the styrene.

[0039] According to another aspect of the invention there is provided a method for producing a composition according to the invention, comprising the steps of providing a resin particle; providing an enzyme, high speed mixing the particle with the enzyme, such that the enzyme attaches to the particle; forming the composition; and optionally, drying the composition.

[0040] As generally used herein, the term “high speed” in the context of “high speed mixing” is typically understood as mixing at rotational speed (rpm) of more than 1000 rpm, preferably about 3500 rpm, whereby the term “about” constitutes plus minus 2500 rpm, preferably 2000 rpm.

[0041] According to this aspect, the resin particle may have any of the features as described herein.

[0042] Preferably, the resin particle is a toner particle or a powder coating, preferably a toner particle, most preferably a dry toner particle and / or wherein said resin particle has a volume average particle diameter between 5 and 30 micrometer. Advantageously, resin particles that are less harmful to the environment could be achieved. Also advantageously, a (desired) loss of microplastic character could be achieved when entering into an environment containing water, while still being functional, e.g. as toner or a powder coating.

[0043] Preferably, the rising particle and the enzyme are mixed at a rotational speed, expressed as revolutions per minute (rpm), of more than 1000 rpm, preferably more than 1500 rpm, even more preferably more than 2000 rpm, even more preferably more than 3000 rpm, such as about 3500 rpm. Advantageously, an improved attachment between said rising particle and enzyme could be achieved. In this manner, deinking capacity is maintained.

[0044] Preferably, the rising particle and the enzyme are mixed at a rotational speed (rpm) between 1000 rpm to 10 000 rpm, preferably between 1500 rpm to 8500 rpm, even more preferably between 2000 rpm to 6500 rpm, even more between 3000 rpm to 5000 rpm, such as about 3500 rpm. Advantageously, a good attachment between said rising particle and enzyme is provided as such, hence deinking capacity could be ensured in an improved manner.

[0045] Preferably, in additional to said rpm or alternatively, the rising particle and the enzyme are mixed at speeds, greater than 10 m / s, preferably greater than 20 m / s, even more preferably greater than 30 m / s, even more preferably greater than 40 m / s, even more preferably greater than 50 m / s. Advantageously, a good attachment between said rising particle and enzyme is provided as such, hence deinking capacity could be ensured in an improved manner.

[0046] In an embodiment, the production of the enzyme-resin composition according to the invention, additionally comprises the step of screening or sieving the composition, thus removing big particles larger than screen holes. This has the advantage of removing larger conglomerates of enzymes, which would otherwise influence the printing / coating capabilities of the electrostatically charged resin. These would show up as large dots of white on a printed substrate. Preferably air jet sieving is used.

[0047] In an embodiment, the provided enzyme is a dried enzyme. This has as advantage that a high concentration of enzyme can be added, and no additional drying step is required. Additionally, this has the advantage that the production process of the enzyme -resin composition can be completely free of liquids.

[0048] In an alternative embodiment, the provided enzyme is an enzyme in solution. This has as advantage that during the preparation of the provided enzyme, no additional drying steps are required. This is especially advantageous when the resin particle is also provided in solution, e.g. for application as a liquid toner or a chemical produced toner. Drying can be performed with any of the known techniques, such as heating the composition to evaporate the liquid, or freeze drying or removing the liquid(s) under reduced pressure. In a particular embodiment of the method for producing a composition according to the invention, the enzyme is provided on the surface of an additive, wherein the step of high speed mixing, preferably mixing at speeds of more than 1000 rpm, comprises mixing the additive-enzyme with the resin particle, such that the additive-enzyme becomes attached to the resin particle. This has as advantage that the additive and enzyme can be added to the particle at the same time.

[0049] Also advantageous is that the enzyme can be evenly distributed across the additives by using the high surface area of the additives, which can result in a more efficient use of the enzyme.

[0050] According to another aspect of the invention there is provided a method for depolymerizing and / or increasing the water solubility of a composition according to the invention, comprising the steps of providing the composition; bringing the composition into contact with water and adjusting the water temperature to a temperature Tw, such that the enzyme either depolymerizes the resin particle and / or increases the water solubility of the resin particle. This has as advantage that the resin will no longer be considered a microplastic, either by making it water soluble, and / or by breaking it down to oligomers and monomers, such that it also become water soluble. Preferably, according to this aspect, the temperature Tw satisfies the condition Tg-D < Tw < Td as described herein. According to another aspect of the invention there is provided the use of the composition according to the invention, and the use of a composition obtained by the method according to the invention in a printing process.

[0051] According to another aspect of the invention there is provided a method for the deinking of a substrate on which a composition according to the invention has been printed. Said method comprises the steps of providing a printed substrate, wherein the printed substrate comprises the composition of any of the previous claims, preferably the resin particle is a toner particle; disintegrating the printed substrate, preferably by shredding or pulping, most preferably by pulping; adding water to the disintegrated substrate; and modifying the water temperature Tw such that the resin particles are catalytically depolymerized and / or the water solubility of the resin particle is increased. By adding enzymes to the initial composition, the energy required for the deinking procedure is lower and the speed will be higher. Additionally, higher temperatures, such as above 40°C, are already commonly used in deinking plants. It will thus not require any additional heating or energy investment, while still speeding up the deinking process.

[0052] A further aspect herein provides a toner container, such as a toner bottle, comprising a composition as provided herein. Advantageously, by including the composition as described herein, the container can be cleaned in an improved manner. Namely, water could be added to the toner bottle and the waste water would not be harmful to the environment, as the toner would have been broken down. This greatly enhances the recyclability properties of the empty toner bottles.

[0053] There is further provide a method for recycling and / or cleaning a toner container wherein the toner container comprises the toner as described herein. The method comprising: washing the toner container with water, preferably heated water, more preferably water at a temperature of more than 25 °C, such as a temperature between 25°C and 75°C (eventually with some light pH increasing assistance by adding some inorganic buffer).

[0054] The temperature of the water is preferably chosen to optimize the cleaning process by effectively dissolving and removing toner residue without damaging the container or causing excessive water and / or energy waste. It is clear that, as disclosed herein, the elements or features of one aspect described herein are usable in other aspect, unless explicitly specified otherwise. For example, the elements or features described in the context of the composition are also combinable with the context of the method(s) as described herein.

[0055] Fig. 1 describes the pH stat monitoring of enzymatic hydrolysis of T1-T4 by measuring the added amount of mmol sodium hydroxide (NaOH).

[0056] Fig. 2 describes the pH stat monitoring of enzymatic engagement by measuring the added amount of mmol sodium hydroxide (NaOH), a polyester based resin toner particle and an acrylate resin based toner particle have been used for monitoring and concluding improved water solubility minitored by the amount of NaOH used to keep the pH constant at 8. The addition of the NaOH is an indirect proof of the hydrolysis of the ester groups in the resin of the toner particle resulting in a water soluble chemical mixture

[0057] Detailed

[0058] The accompanying drawings are used to illustrate presently preferred non-limiting exemplary embodiments of devices of the present invention. The above and other advantages of the features and objects of the invention will become more apparent and the invention will be better understood from the following detailed description. RESIN

[0059] The terms resin, particle, polymeric resin particle, polymeric resin, polymeric particle, or any combination of these words are all used interchangeably in the present invention.

[0060] A polymeric resin particle or a polymer segment in the context of the present invention is defined as a large molecule, or macromolecule, composed of many repeated subunits. In particular, a polymer may be characterized by the sequence of one or more types of monomer repeating units which are covalently bonded to at least five other monomer repeating unit. Thus, a polymer segment has a sequence comprising six or more repeating units. In the context of this definition a repeating unit means the reacted form of a monomer in the polymer.

[0061] In the context of the invention, an oligomer is defined as a sequence of two to five monomer repeating units. In the context of this definition a repeating unit means the reacted form of a monomer in the oligomer.

[0062] Any resin particle that comprises a composition that can be modified by an enzyme, can be used in the invention.

[0063] Generally herein, the resin particle is may be chosen from a polyester based resin toner particle and an acrylate resin based toner particle. In this manner, desired printing properties can be achieved while ensuring a good deinking and a desired loss of microplastic character.

[0064] The resins according to the invention are not water-soluble, or water-insoluble, in the absence of enzymes. Resins are considered water-insoluble if the solubility of the resin is lower than 10 g / L in water at 20°C .

[0065] Preferably, the resin particle comprises one or more hydrolysable groups in its backbone structure, such as polyesters, such that the polymer is broken down in smaller segments, and thus becomes water soluble.

[0066] Alternatively, the resin particle preferably comprises one or more groups in its backbone structure such that the backbone becomes water soluble upon hydrolysis, such as polyacrylates or polyvinylacetates. Making the polymer water soluble through the action of an enzyme, also results in avoiding that microplastics end up in the environment. Water soluble polymers are not considered microplastics, while non-soluble polymers are considered microplastics.

[0067] Alternatively, the resin particle comprises a composition that can be oxidized, catalyzed by an enzyme and a suitable cofactor, such as a styrene butadiene resin composition. By breaking down the backbone of the polymer, the resin breaks down in smaller segments, such as monomers. However, catalytic oxidation has the drawback of the need for cofactors in addition to the enzymes, and are thus less preferred than hydrolyzable resin particles.

[0068] In an exemplary embodiment, the polymer segment may comprise at least one of an alkyleneoxide group, an olefin group, an ester group, an amide group , an urethane group, an acrylic group, a styrene group, a butadiene group, a vinylic group, a vinylether group, a vinylester group, and / or a vinylamide group.

[0069] Alternatively or additionally, the polymer segment may comprise a polyacrylic group and / or a polymethacrylic group and / or a polyurethane group.

[0070] Alternatively or additionally, the polymer segment may comprise a polyolefin polymer, which is partially modified by an amine, hydroxyl, and / or ester group, such as NucrelTM polymers. Said amine modified polyolefin polymer may be a polyethylene polymer or a propylene polymer, which is amine modified. Such an amine modified polyolefin polymer is also known as a long-chain alkylpoly amine. A long-chain alkylpoly amine is preferably used for a positively charging system. Alternatively or additionally, the polymer segment may comprise a polyethylene polymer or a propylene polymer, which is acid modified or alcohol modified, such as Unilin™, Unicid™ and Ceramer ™ products obtainable from Nucera (previously Baker Hughes).

[0071] Examples of resin particle polymers according to the invention comprise polyester, polyether, polyolefin, polyurethane, styrene resin, a styrene- acrylic resin, a styrene -butadiene resin, an epoxy resin, polyacrylate, and / or polyester acrylate, preferably polyester.

[0072] The size of the electrostatically chargeable polymeric resin particle is defined by its volume average particle diameter. Said diameter can be measured via a Coulter counter or via a laser diffraction analyzer, preferably a Coulter counter as measurements via laser diffraction might display so-called “ghost fractions”. Alternatively, particle size could be determined with e.g. microscopy techniques, all known to the person skilled in the art.

[0073] A Coulter counter is an analytical apparatus that can measure particle size by detecting changes in electrical impedance. The particles are suspended in a solution with electrolytes. The presence of the electrolytes make the solution conductive. An electric field is applied between two electrodes with an aperture and the electrical impedance between these two electrodes is measured. The solution is mixed, and as particles pass by through the aperture, the electrical impedances between the electrodes changes which can be measured as a voltage pulse or a current pulse. The volume of the particles cause displacement of electrolyte which induce the change in electrical impedance. The number and volume of the particles can be determined based on these measurements, and the equivalent spherical diameter can be calculated. The suspended particles need to be poorly conductive to be able to determine the correct particle size. Depending on the aperture size, particle size can be measured in the range of 0.4 - 1600pm.

[0074] The particle size is dependent on the foreseen application. For example, for a powder coating application, the diameter is preferably in the range of 10 to 120 pm, more preferably in the range of 20 to 90 pm. On the other hand, toner particles useful in this invention can have an average volume diameter (size) between 5 to 30 micrometer, preferably between about 5 and 20 pm. When the toner particles are intended for use in color imaging, it is preferred that the volume average diameter is between 5 and 12 pm, most preferred between 5 and 10 pm. The particle size distribution of said toner particles can be of any type. It is however preferred to have an essentially Gaussian or normal particle size distribution, either by number or volume, with a coefficient of variability (standard deviation divided by the average) (v) smaller than 0.5, more preferably of 0.3. Some negative or positive skewness of the distribution can be tolerated, although a positive skewness, giving less smaller particles than an unskewed distribution, is preferred. Notably, pm, micrometer or micrometre are used interchangeably herein.

[0075] TONER

[0076] In the case wherein the polymeric resin particle is a toner particle, toner particles according to the present invention can be prepared by any method known in the art.

[0077] Those toner particles can be prepared by melt kneading or extruding the toner ingredients (e.g. toner binder resin(s), charge control agent(s), pigment(s), etc). After the melt kneading or extrusion, the mixture is cooled and the solidified mass is pulverized and milled, and the resulting particles classified. After the classifying step, an optional rounding step may be performed followed by the mounting of optional surface additives. Alternative methods of producing toner may also be used, such as with the use of chemical processes (emulsion aggregation or in situ polymerization).

[0078] Toner particles, useful in this invention, can comprise any normal toner ingredient e.g. coloring agents e.g. pigments or dyes both colored and black, inorganic fillers, anti-slip agents, flowing agents, waxes, etc.

[0079] Toners for the production of color images may contain organic dyes / pigments of for example the group of phthalocyanine dyes, quinacridone dyes, triaryl methane dyes, sulfur dyes, acridine dyes, azo dyes, and fluorescein dyes. Also TiO2, ZnS or BaSO4 can be used as a pigment to produce white toners. In order to obtain toner particles with sufficient optical density in the spectral absorption region of the colorant, the colorant is preferably present therein in an amount of at least 1 % by weight with respect to the total toner composition. To improve the distribution of the colorant in the toner resin, it may be beneficial to add a so-called master batch of the colorant during the toner preparation instead of adding the pure colorant. The master batch of the colorant is prepared by dispersing a relatively high concentration of the colorant, present as pure pigment or as press cake, preferably ranging from 20 to 50% by weight in a resin, e.g. a polyester. The same master batch techniques can also be used for dispersing charge control agents and photo initiators, if present. Positive and negative charge control agents (CCA) can be used to adjust the triboelectric chargeability of a chargeable toner composition in either negative or positive direction. In an exemplary embodiment, the chargeable toner composition is negatively chargeable. Typically, metal complexes of one or more salicylates can be used as negative charge control agents.

[0080] In particular, a charge control agent based on a metal compound is particularly advantageous as it may be substantially colorless. In fact, prior art charge control agents based on metal complexes of salicylate, such as Bontron E84 and Bontron E88 (both ORIENT CHEMICAL - MITSUI), are found to be suitable for color applications because they are colorless. Alternatively, polymeric CCAs can be used.

[0081] ENZYME

[0082] Any enzyme that is able to depolymerize and / or make water soluble the corresponding polymer of the resin particle is suitable. For example, a polyether resin requires an enzyme that is able to catalytically depolymerize polyether into monomers and / or oligomers.

[0083] An enzyme is a protein that can act as a catalyst. An enzyme in the context of the present invention could be any enzyme that is able to modify the corresponding resin polymer, such that the resin polymer becomes not or less harmful to the environment. It is clear to the skilled person that enzymes have specific substrates; one will thus be able to choose an appropriate enzyme for each polymeric resin.

[0084] Examples of enzymes are plentiful, as these can nowadays largely be engineered or commercially bought. An example is Novozym 51032, a lipase originating from Aspergillus, which is known for catalytic hydrolysis of ester bonds of triglycerides. Other enzymes would e.g. be Lipozyme® TL 100 L, a 1,3 specific lipase originating from Thermomyces lanuginosus. Other alternatives include leaf-branch compost cutinase (LCC), Ideonella sakaiensis PETase (IsPETase) Suberase and Candida antarctica lipase B (CALB).

[0085] Other enzymes can be engineered by methods as described in e.g. Zhu, B., Wang, D. and Wei, N., 2022. Trends in biotechnology, 40( ), pp.22-37, or enzymes suitable in different fields, e.g. for the breakdown of polyester clothing. Suitable enzymes, mentioned in said document and incorporated herein by reference, are enzymes chosen from a group including PETase, PET hydrolase, cutinase, esterase, lipase, protease, polyurethane esterase, PHB depolymerase, polyamidase and haloalkane dehalogenase. Enzymes suitable to be used are hydrolases, ligases, lyases, oxido-reductases, transferases, isomerases, kinases. According to a preference herein, the enzyme is chosen from a hydrolase or a lipase. It is furthermore desirable to choose an enzyme which has a relatively low optimal working temperature. As a result, heating will not be required or the need for heating will be strongly reduced. Degradation of the polymer in the presence of an enzyme with a low working temperature will thus result in a cheaper process than when another enzyme or no enzyme is used in the degradation process. Compared to enzymes with higher optimal working temperatures, the catalytic depolymerization will be faster at e.g. room temperature.

[0086] The catalytic activity of an enzyme is strongly dependent on the temperature. A low temperature results in a low activity, which increases as the temperature increases. However, at a certain temperature (Td), the enzyme may lose its structure and unfold, a phenomenon called denaturation. To break down the particles, the composition should preferably be brought to a temperature wherein the enzyme is active, thus high enough for a noticeable increase in catalytic activity, but low enough such that the enzyme is not denatured.

[0087] The enzymes can be attached to the polymer resin either directly or indirectly. By mechanically mixing the resin and the enzyme, the enzyme attaches directly to the resin’s surface. The attachment happens through a van der Waals interaction and / or Coulomb attraction. Alternatively, the enzyme can be added to the surface of any of the additives, thus being added indirectly to the polymer resin.

[0088] The enzyme could be added to an additive particle prior to the mounting on the surface of the resin particle in the same way as described above. A mixture of the enzyme and the additive could be created followed by removal of the liquid and subsequently adding the additive (with the enzyme on its surface) as powder additive.

[0089] The adhesion of the enzyme is done in the same way as the additives are added and consists of a mixture of van der Waals forces and triboactivity resulting in a Coulomb attraction - this is for adding the enzyme to a powder particle in dry conditions using high speed additive mixing equipment. As mentioned before the enzyme could be added to an additive particle prior to the mounting on the surface of the resin particle. It should be understood that adding the enzymes to the additive particles before addition to the particle surface, only works in case the van der Waals adhesion to this additive is not so high that it does not block permanently the active site of the enzyme.

[0090] Alternatively, the enzyme can be added by dissolving the enzyme in water and add the resin particle to it, followed by removing the water so the enzyme is concentrated and dried onto the surface of the particle.

[0091] CATALYTIC POLYMER MODIFYING PROCESS

[0092] PRODUCTS

[0093] It is an object of the invention to provide a composition that can be modified into non-toxic components. These non-toxic components are components that are not harmful to the environment and can be used and / or metabolized by organisms present in nature. This is done by bringing the composition in contact with water and adjusting the temperature such that the enzyme modifies the resin particle into non-toxic components. It depends on the type of polymer of the resin what these non-toxic and / or water soluble components are. Some polymers, should be broken down into at least oligomers, as both monomers and oligomer building blocks of these polymers are not harmful to the environment. Other polymers, the resin needs to be broken down to its monomers, as longer molecules, such as oligomers, would accumulate in the environment and might thus still be considered a microplastic and thus toxic to nature. The acceptable final residual chain length, being monomers or oligomers, strongly depends on the ability of the oligomer / monomer to be dissolved in water. Generally, more hydrophilic oligomers will more easily dissolve in water, and will thus be non-toxic. It is thus not necessary to continue the depolymerization reaction until all polymer is broken down into monomers. However, more hydrophobic oligomers will less easily dissolve in water, and will thus need to be broken down even further, even until only monomers are left. The skilled person will be able to determine the length of the acceptable final residual chain. Generally, this will either be monomers, dimers and / or trimers.

[0094] Alternatively, the polymer does not need to be broken down to monomers or oligomers, but could be modified such that the polymer itself becomes water soluble, and thus non-toxic. An example is a polyacrylate.

[0095] The polymer-modification reaction can be followed with a variety of techniques. In a controlled reaction, the pH can be kept constant by the addition of sodium hydroxide (NaOH) or another suitable base, and the amount of added NaOH can be continuously measured, also known as pH- stat. Alternatively or additionally, at set times, the concentration of polymers, oligomers and monomers can be determined via e.g. liquid chromatography-mass spectrometry (LC-MS) or other methods, known to the person skilled in the art. Other methods for following the reaction are known to the skilled person.

[0096] TEMPERATURE

[0097] The water in which the composition is placed, is adjusted to a temperature above 20 degrees Celsius below a glass temperature Tg of the composition, preferably 15 degrees below a glass temperature (Tg) of the composition, more preferably 10 degrees below a glass temperature Tg of the composition, and most preferably 5 degrees below a glass temperature Tg of the composition, such that the modification of the resin particle in the composition is accelerated. It is expected that the temperature of the water closely corresponds the temperature of the composition when this composition is in the water, or at least corresponds to the temperature on the surface of the composition. Generally, the Tg is preferably measured with Differential Scanning Calorimeter (DSC Q20 from TA Instruments), heating rate 20°C / min, 2 heating cycles, the Tg is then determined in 2ndheating step, by half height of the height in slope of the thermogram. The terms glass temperature, glass temperature and Tg are used interchangeably herein.

[0098] It is generally known that enzymes are biological catalysts and thus have an optimal working temperature. It was found that the speed of the catalytic depolymerization of the polymeric resin by the enzyme depends on the glass temperature of the composition comprising the polymeric resin. A noticeable effect in reaction time is observed when the water surrounding the composition is heated to at least 20 degrees Celsius below the Tg. As expected, the higher the temperature, such as 15, 10 or 5 degrees Celsius below Tg, the faster the depolymerization or modification reaction occurs, as this gets closer to the optimal working temperature of the enzyme. The temperature does not need to be below the Tg of the composition, but can also be at, or above the Tg.

[0099] On the other hand, the denaturation temperature (Td) of the enzyme always needs to be considered as a maximum temperature, such that the enzyme is not denatured. As the enzyme would lose its conformation and thus its functionality, it is a requirement that the temperature is kept below said denaturation temperature.

[0100] As enzymes can nowadays be engineered, there is a wide range on the denaturation temperatures of the enzymes. Generally, enzymes would denature between 40 and 55°C, but specifically engineered enzymes have denaturation temperatures of 100°C and higher.

[0101] Generally, the water will need to be heated to adjust the temperature to above room temperature and to reach the required temperature. However, for compositions with very low Tg, it is possible that heating is not required, or even cooling is possible.

[0102] It was further determined by the inventors that the minimal temperature for the catalytic depolymerization or modification depends on the glass transition temperature (Tg) of the composition. It is further understood by the inventors that a certain mobility of the resin is required in order to have the right conformation to approach the active site of the enzyme so that the intended reaction can take place.

[0103] Typical glass temperatures (Tg) of composition are in the range of 40-80 °C. However, other composition with a different resin composition might have lower or higher Tg, depending on the composition.

[0104] The Tg of the composition should be understood to constitute the Tg of the whole composition, in the case of a homogenous resin. Alternatively, when the resin in the composition is non- homogenous, for example comprising a core-shell particle, the Tgs of the different polymers in the composition should be considered. The temperature of the surrounding water should be chosen in function of the polymer with the highest glass temperature, e.g. when the Tg of the shell resin is higher than the Tg of the core resin, the water temperature should be chosen in function of the Tg of the shell resin. The Tg of the composition comprising a core-shell particle is usually mostly influenced by the Tg of the shell.

[0105] In the case of a non-homogenous polymer particle, it should further be determined whether it is desirable that all polymers are broken down or modified, which will often be the case. In that case, enzymes need to be added to the composition that can depolymerize or modify each layer. This can be achieved by attaching an enzyme that has catalytic activity against all polymers present in the particle. Alternatively, a mixture of enzyme types can be added, so that for at least all polymer layers that need to be broken down or modified, an enzyme is present that is capable of depolymerizing or modify said layers. Obviously, one should take care that the ratio of enzyme to polymer is high enough for each type of polymer, while still making sure that the final application, e.g. printing with toner, is still of satisfactory level.

[0106] The Tg of the final composition, such as a toner composition, is generally somewhat lower than the Tg of the polymeric resin. This is due to the fact that some ingredients can have a plasticizing effect when a mixture of resin is used.

[0107] WATER FASTNESS AND DEINKING

[0108] The water fastness of the printed / coated object is not influenced by the addition of the enzyme. It was determined by the inventors that after fixing toner on a substrate, the toner did not always dissolve when the substrate was covered with water, even upon heating the system. Without wishing to be bound by theory, it is speculated that the access of enzymes to the water is too limited after printing: many enzymes will be on the inside of the printed toner layer, and will thus not be into contact with the water and will thus not be able to act as a catalyst.

[0109] When higher concentrations of enzymes are added to the toner, enzymes are still able to depolymerize or modify the toner. A drawback of using a higher ratio of enzymes / toner is that the printing results might suffer, as less toner is used.

[0110] The enzymes in the printed enzyme-toner composition may still aid in a deinking process. During deinking, e.g. enzymatically, an increasing amount of enzymes will again become available to depolymerization the toner because the ink / toner layer is broken down in small parts during the pulping of the paper or the milling of plastic substrates, and will thus strongly increase the speed and efficiency of the deinking without the need to add additional deinking chemicals to the mixture.

[0111] If water fastness of the printed / coated object is not a priority, it is possible to choose an enzyme with an extremely high kinetic activity, even at low catalytic concentrations. This would result in a lower water fastness of the object at higher temperature (not below Tg-20°C), but much better deinking properties at the deinking temperature of 40-60°C with a Tg of the toner system around that range.

[0112] Examples

[0113] TONER COMPOSITION PREPARATION

[0114] The toner compositions T1 - T4 and T5 were prepared by melt blending for 30 minutes in a laboratory kneader at 100 °C. The ingredients include the charge control agents and other additives as indicated in Table 2, together with 3% by weight of a phthalocyanine blue pigment as mentioned in Table 1. The indicated mass% is the mass% based on the weight of the toner composition.

[0115] After cooling, the solidified mass was pulverized and milled using an Alpine Fliessbettgegenstrahlmuhle 100AFG (Hosokawa Alpine) and further classified using a multiplex zig-zag classifier type 100MZR (Hosokawa Alpine) to obtain a toner with a Dv50 between 7 and 9 pm.

[0116] Additives in about 0.2% can be added. Advantageously, a rotational speed (rpm) of about 3500 rpm resulted in a good attachment between the enzyme component and the resin particle. In the second step, 0.7% hydrophobized TiO2 was added at 3500 rpm for 2 minutes. In the third step, 0.75% hydrophobized SiO2 was added at 3500rpm for 2 minutes. For T2 and T4, in the fourth and final step, 0.25% of the solid dry enzyme was added at lOOOrpm for 2 minutes. For T3, the enzyme was added to the toner without high speed mixing (e.g. mixing at a speed equal or below 1000 rpm), therefore the enzyme was not bound to the surface of the toner particles. For Tl, no enzyme was added.

[0117] After adding the surface additives and enzyme, the final toner Tl and T2 were screened / sieved with air jet sieving to remove coarse particles. With air jet sieving, particles are sieved by moving particles over a sieve mesh while air streams keep the particles in the air and subsequently the particles are pulled over the sieve mesh by a vacuum.

[0118] Table 1 - toner compositions, ingredients are shown in mass% of the toner composition

[0119] The enzyme used is Novozym51032 (Novozymes A / S), a commercial species of Thermomyces insolens lipase (TiL), formerly known as Humic ola insolens (HiC), which is a lipase known for catalytic hydrolysis of ester bonds of triglycerides. The solid enzyme was obtained by precipitating the enzyme from the Novozym51032 solution with isopropanol. After precipitation, the enzyme was further separated through filtration. Preferably, the enzyme is chosen from a lipase.

[0120] DEVELOPER PREPARATION

[0121] From toners T1 to T4 developers were prepared by mixing said toner particles together with coated silicone MnMgSr ferrite carrier with a Dv50 of 50 pm in a ratio of 7 / 100. Images were developed on a laboratory scale developing unit and fused with a contact fuser. The fusing temperature of the contact fuser was set at 95 °C for the prefix roller (heating backside of substrate) and 130°C for the fuser roller (contact with printed toner). As used herein, Particle Size Distribution D50 is also known as the median diameter or the medium value of the particle size distribution, it is the value of the particle diameter at 50% in the cumulative distribution. It is one of an important parameter characterizing particle size. For example, if D50=5.8 um, then 50% of the particles in the sample are larger than 5.8 um, and 50% smaller than 5.8 um. D50 is usually used to represent the particle size of group of particles. Dv50 is also known as volume median or volume average particle size, it physically represents that each volume of particles greater or smaller than such value takes account of 50% of the total particles volume. CATALYTIC DEPOLYMERIZATION

[0122] The monitoring of enzymatic hydrolysis is done by pH-stat. The temperature was increased every 30 minutes, starting at 30°C to 65°C in steps of 5°C, and then kept at 60 or 65°C. The temperature was controlled with a Proportional-Integral-Derivative (PID) controller and heat mantle. The amount of NaOH that was added to keep the pH at 8 was measured as a parameter for enzymatic hydrolysis. An increase in the amount of added NaOH indicates an increase in enzymatic hydrolysis. A 20mL solution of water and lOOmg of toner was placed in a 60mL bottle and the amount of added NaOH was monitored for 70,000s. The pH, temperature, pump speed and other parameters were logged every 10 seconds.

[0123] LC / MS (Agilent) was used for characterization of the monomer / oligomers.

[0124] Results temperature. In Table 2, an X signifies that no 100% conversion to monomers and oligomers was observed, while a V signifies that 100% conversion occurred.

[0125] Table 3: Printing results. In Table 3, values between 1 and 5 are attributed to the charging, printing and fusing parameters. 5 indicates the optimum, while 1-2 are not acceptable.

[0126] Depolymerization results can be found in Table 2 and Figure 1. At a temperature below 30°C below the glass temperature of the toner particle, here 20°C, no noticeable enzymatic activity was observed. At a temperature of 20°C below the glass temperature of the toner particle, here 30°C, enzymatic depolymerization commenced. As expected, the enzymatic rate increased upon increasing the temperature.

[0127] Sample Tl, without any enzyme present, did show that a low amount of NaOH was consumed. It is speculated that this is due to the reaction of the carboxylic acid groups of the polyester of the resin, with the NaOH. LC-MS confirmed that sample T1 was not broken down into monomers and / or oligomers.

[0128] A mixture of toner with enzymes, while the enzymes are not bound to the surface of the toner resin, sample T3, was found to exhibit superior depolymerization characteristics. This could also be partly due to the fact that a higher amount of enzyme was added. As can be derived from Table 3, these mixtures do not give satisfying printing results. It is speculated that the enzymes are visible as white dots on the printed substrate, and thus are not suitable for high quality applications. However, in other applications than toner printing, such mixtures might also be appropriate, as the quality requirements might be lower.

[0129] Example T4, which differs from T2 in the additional step of sieving, is somewhat worse than T2. This can be attributed to the additional airjet sieving step.

[0130] Analysis with LC-MS confirmed that the resin was indeed broken down into monomers and oligomers. It was further concluded that the same results are contemplated and achievable for both toner and powder coating resin particles.

[0131] WATER SOLUBILITY OE THE RESIN PARTICLE INCREASES

[0132] An experiment has been conducted which indicates that the polymer-modifying enzyme (lipase) is able to increase the water solubility of the polymeric resin particle(s). The average particle diameter for the resin particle was between 5 and 120 micrometre, in particular between 5 to 30 micrometre. Specifically, a polyester based polymeric resin (toner) and a styrene acrylate polymeric resin (toner), also described as styrene acrylic (sample T5) was tested and reviewed (see e.g. Fig. 2). The following contemplations are made.

[0133] Table 5

[0134] For the polyester based toner, the enzyme caused a breakdown of the polymeric backbone (likely due hydrolysis) which resulted in mono and oligomers. Consequently, the water solubility of the polyester based resin increased because the polymeric character of the resin / toner disappears. Notably, such breakdown behaviour is beneficial for losing microplastic character when entering into an environment containing water.

[0135] For the styrene-acrylate toner, the enzyme affects the acrylate portion (ester) to form acid groups which have a more hydrophilic character. Consequently, the water solubility of the acrylate resin increased. Notably, such breakdown behaviour is beneficial for losing microplastic character when entering into an environment containing water. Thus, the inventors concluded that the attached enzyme is capable of increasing the water solubility of the polymeric resin particle (including the embodiments whereby the resin is a toner or dry powder coating particle). More in particular, the attached enzyme is capable of increasing the water solubility of toner particles in a highly desired manner.

[0136] The average particle diameter

[0137] The following is contemplated with respect to volume average particle diameter for the toner and dry coating composition.

[0138] Table 6

[0139] Industrial applicability

[0140] Understandably, the examples above are for illustrative purposes. Generally, it has been found that by using enzyme and by attaching said enzyme to the resin particle, the resin particle can be used for its purpose (e.g. used in a toner or powder coating composition, preferably for use in a printing process). In case the resin comes into contact with water, e.g. in case of an accident with transport overseas, the resin will be degraded and will not be harmful to the environment, such as marine life.

[0141] Additionally, the property of water degradability could be used to clean out toner containers, e.g. toner bottles more thoroughly. After sucking the toner bottles dry, heated water could be added to the toner bottle. The waste water would not be harmful to the environment, as the toner would have been broken down to monomers and oligomers. This greatly enhances the recyclability properties of the empty toner bottles. Furthermore, deinking speed of polymeric substrates and paper substrates will be improved.

[0142] Hence, there is further provided a method for recycling and / or cleaning a toner container comprising the toner and / or powder coating composition as described herein, the method comprising: washing the toner container with water, preferably heated water, more preferably water at a temperature of more than 25 °C, such as water with a temperature in the range of 25 - 75 °C. The method for recycling and / or cleaning, thereby typically includes letting the enzyme for depolymerize and / or dissolve the polymeric resin particle. In this manner, the microplastic character is lost when entering into an environment containing water.

Claims

Claims1. A toner or a powder coating composition, comprising- an electrostatically chargeable polymeric resin particle, wherein the resin particle has a volume average particle diameter between 5 and 120 micrometer as measured with a Coulter counter, wherein the resin particle is a toner particle or a powder coating, preferably a toner particle, most preferably a dry toner particle; and- an enzyme, wherein the enzyme is a polymer-modifying enzyme for depolymerizing and / or increasing the water solubility of the polymeric resin particle, wherein the enzyme is attached to a surface of the resin particle.

2. A composition comprising a. an electrostatically chargeable polymeric resin particle with a volume average particle diameter between 5 and 120 micrometer; wherein the volume average particle diameter is measured with a Coulter counter; wherein the resin particle is a toner particle or a powder coating, preferably a toner particle, most preferably a dry toner particle; and b. an enzyme; wherein the enzyme is attached to a surface of the resin particle; wherein the enzyme is a polymer-modifying enzyme capable of catalytically depolymerizing the resin particle into monomers and / or oligomers upon bringing the composition into contact with water at a water temperature Tw at which the enzyme is capable of depolymerizing the resin particle into monomers and / or oligomers; and / or catalytically modifying the resin particle such that the water solubility of the resin particle increases, upon bringing the composition into contact with water at a water temperature Tw at which the enzyme is capable of modifying the resin particle; satisfying the following conditionTg-D < Tw < Td whereinTg = glass transition temperature of the composition, wherein said Tg is preferably measured with Differential Scanning Calorimeter (DSC Q20 from TA Instruments), heating rate 20°C / min, 2 heating cycles, the Tg is then determined in 2ndheating step, by half height of the height in slope of the thermogram;Tw = temperature of the water;Td = denaturation temperature of the enzymeD = 20 °C, preferably 15 °C, more preferably 10 °C, most preferably 5 °C.

3. The composition according to any of the previous claims, wherein the resin particle comprises any of a polyester, polyether, polyolefin, polyurethane, polyester acrylate, polyacrylate and / or styrene-butadiene copolymer, preferably polyester, polyether and / or polyacrylate, most preferably polyester.

4. The composition according to any of the previous claims, wherein the polymer-modifying enzyme is capable of catalytically depolymerizing the resin particle into monomers and / or oligomers of a length of two to three monomers, preferably into monomers.

5. The composition according to any of the previous claims, wherein the polymer-modifying enzyme is capable of hydrolyzing the resin particle.

6. The composition according to any of the previous claims, wherein the enzyme is chosen from the group consisting of: esterase, protease, hydrolase, lipase, ligase, cutinase, PETase, PET hydrolase, polyurethane esterase, lyases, oxido-reductase, transferase, isomerase, kinase, haloalkane dehalogenase.

7. The composition according to any of the previous claims, wherein the mass ratio of the enzyme to the resin particle is between 0.05 % and 8.0 %, preferably between 0.1 % and 5.0 %, more preferably between 0.2 % and 2.0 %.

8. The composition according to any of the previous claims, wherein the enzyme is attached to the surface of the particle via van der Waals force and / or Coulomb force.

9. The composition according to any of the previous claims, wherein the composition is a toner composition.

10. The composition according to any of the previous claims, wherein the resin particle is a toner particle having a volume average particle diameter between 5 and 30 micrometer.

11. A toner container, such as a toner bottle, comprising a composition according to any of any of the previous composition claims.

12. A method for recycling and / or cleaning a toner container according to the previous claim, the method comprising: washing the toner container with water, preferably heated water, more preferably water at a temperature of more than 25 °C.

13. A method for producing a composition comprising a resin particle and an enzyme, said method comprising the steps of:- providing a resin particle, preferably the resin particle is a toner particle or a powder coating, preferably a toner particle, most preferably a dry toner particle;- providing an enzyme, wherein the enzyme is a polymer-modifying enzyme for depolymerizing and / or increasing the water solubility of the polymeric resin particle- high speed mixing the particle with the enzyme, such that the enzyme attaches to the particle; preferably wherein said high speed mixing comprises mixing the particle with the enzyme at a rotational speed (rpm) of more than 1000 rpm;- forming the composition; and optionally, drying the composition.

14. The method according to the previous method claim, additionally comprising the step of a) screening the composition, preferably airjet sieving the composition.

15. The method according to any of the previous method claims, wherein the provided enzyme is a dried enzyme.

16. The method according to any of the previous method claims, wherein the provided enzyme is an enzyme in solution.

17. The method according to any of claims any of the previous method claims, wherein the enzyme is provided on the surface of an additive, wherein the step of high speed mixing comprises mixing the additive-enzyme with the resin particle, such that the additiveenzyme becomes attached to the resin particle, particularly wherein said high speed mixing comprises mixing at a rotational speed (rpm) of more than 1000 rpm, preferably between1000 rpm to 10 000 rpm, preferably more 1500 rpm to 8500 rpm, even more preferably more 2000 rpm to 6500 rpm, even more preferably 3000 rpm to 5000 rpm, such as about 3500 rpm.

18. A method for depolymerizing and / or increasing the water solubility of a composition according to any of the previous composition claims, comprising the steps of: providing said composition; bringing the composition into contact with water and adjusting the water temperature to a temperature Tw, such that the enzyme: depolymerizes the resin particle; and / or increases the water solubility of the resin particle.

19. The method according to the previous claim, wherein the temperature Tw satisfies the following conditionTg-D < Tw < Td whereinTg = glass transition temperature of the composition,;Tw = temperature of the waterTd = denaturation temperature of the enzyme,D = 20 °C, preferably 15 °C, more preferably 10 °C, most preferably 5 °C.

20. The method according to any of the previous method claims, wherein the resin particle has a volume average particle diameter between 5 and 120 micrometer as measured with a Coulter counter.

21. The method according to any of the previous method claims, wherein the resin particle is a toner particle, preferably having a volume average particle diameter between 5 and 30 micrometer.

22. Use of the composition according to any of the previous composition claims, or a composition obtained by the method according to any of the previous method claims in a printing process.

23. Method for deinking a printed substrate, comprising the steps ofa. providing a printed substrate, wherein the printed substrate comprises the composition of any of the previous composition claims, preferably wherein the resin particle is a toner particle; b. disintegrating the printed substrate, preferably by shredding or pulping, most preferably by pulping; c. adding water to the disintegrated substrate; and d. modifying the water temperature Tw such that the resin particles are catalytically depolymerized and / or the water solubility of the resin particle is increased.

24. The method for deinking a printed substrate according to the previous claim, wherein the temperature Tw satisfies the following conditionTg-D < Tw < Td whereinTg = glass transition temperature of the composition, Tw = temperature of the waterTd = denaturation temperature of the enzymeD = 20 °C, preferably 15 °C, more preferably 10 °C, most preferably 5 °C.

Images