Patent Description:
3D printing of plastic materials is a fast-evolving technology. In 3D printing, also referred to as additive manufacturing, the movement of a printing head with respect to the substrate is performed under computer control, in accordance with build data that represent the 3D article to be printed. The build data are obtained by slicing the digital representation of the 3D article into multiple horizontal layers. Then, for each layer, the computer generates a build path to form the 3D article.

Various technologies have been developed for the additive manufacturing of plastic objects, such as extrusion-based processes, powder bed fusion, selective laser sintering, etc..

Extrusion-based additive manufacturing is 3D printing process in which the molten plastic material is selectively dispensed through a nozzle or an orifice. The extrusion-based 3D printing process can be a filament-based process, in which the plastic material is fed to the 3D printer in the form of a filament, or a pellet-based process, wherein the plastic material is fed to the printing device in pelletized form.

The first layer of the printed plastic material solidifies and bonds to the printing platform of the 3D printer. The bond between the printed plastic material and the printing platform should be sufficiently strong to hold the material in place, preventing any displacement during the addition of the subsequently printed layers.

Insufficient adhesion of the printed material to the printing platform can lead to premature detachment and/or slippage of the printed layers, resulting in a flawed structure of the printed article.

In contrary, a strong adhesion between the printed material and the printing platform can prevent premature detachment of the material from the plate. Furthermore, a sufficient adhesion of printed material can prevent warping due to thermal shrinkage, which causes especially the corners of printed articles to lift and detach from the printing platform, leading to deformation of the articles.

At the completion of the printing process, the 3D printed article is generally removed from the printing platform. The easier the printed plastic material can be removed from the printing platform, the less the 3D printed article will be deformed or damaged by removal.

Typically printing platforms are made of glass or metal. Different flexible materials and coatings are known in the art for use as printing plates to cover the printing platform of 3D printers, the flexible material or coating being specifically adapted to the plastic material to be printed onto it.

Disadvantageously, a change of printing material brings about a change of the printing plate material or coating. Furthermore, some printing plates or coatings are sticky and leave sticky residues on printed articles, which must be laboriously removed.

Polyolefins, such as polypropylene and polyethylene, are emerging as printing materials in extrusion-based additive manufacturing. Developing a suitable printing plate, with a good balance adhesion/detachability, that performs also at elevated temperatures on heated printing platforms, is particularly challenging because printed articles obtained from polyolefins generally have a pronounced tendency to warp and therefore require strong adhesion of the printed article to the printing plate.

Printing plates based on <NUM>-butene copolymers with ethylene and/or higher alpha-olefins and suitable for use with a printing material based on polypropylene, nylon, ABS or PLA are known from the international patent application <CIT>.

The international patent application <CIT> discloses a printing plate comprising a propylene-based heterophasic composition, the plate being suitable for printing material based on polypropylene, nylon, ABS or PLA.

In this context, there is still a need of a printing plate for extrusion-based additive manufacturing having an optimized balance adhesion/detachability, i.e. securing a good adhesion between the printing plate and printed material and being easily removable from the printed article, without deforming the article and/or without leaving sticky residues on it.

The present disclosure provides the use of film or sheet comprising a polymer blend obtained by melt blending a mixture comprising:.

In a further aspect, the present disclosure provides an extrusion-based additive manufacturing process comprising selectively depositing a molten thermoplastic material (P) on a film or sheet according to the present disclosure.

In a further aspect, the present disclosure refers to a 3D printing kit comprising:.

When used as printing plate in a extrusion-based 3D printing process, the film or sheet secures the stability of different types of printing material on the printing platform, in particular of printing materials comprising a polyolefin.

Moreover, the film or sheet is easily removable (peelable) from the printed article, without deforming the article and/or without leaving tacky residues on it.

While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description. As will be apparent, certain embodiments, as disclosed herein, are capable of modifications in various obvious aspects, all without departing from the spirit and scope of the claims as presented herein. Accordingly, the following detailed description is to be regarded as illustrative in nature and not restrictive.

In the context of the present disclosure;.

The component (A) is preferably selected from propylene homopolymers, propylene copolymers and propylene heterophasic polymers. More preferably, component (A) is a propylene polymer selected from propylene homopolymers or propylene copolymers with at least one alpha-olefin of formula CH<NUM>=CHR, where R is H or a linear or branched C2-C8 alkyl, the copolymer comprising up to <NUM>% by weight, preferably <NUM>-<NUM>% by weight, more preferably <NUM>-<NUM>% by weight, based on the weight of (A), of units deriving from the alpha-olefin.

The alpha-olefin is preferably selected from the group consisting of ethylene, butene-<NUM>, hexene-<NUM>, <NUM>-methyl-pentene-<NUM>, octene-<NUM> and combinations thereof, ethylene being the most preferred.

In a preferred embodiment, the component (A) is a propylene homopolymer.

The component (A), in particular the propylene homopolymer, has at least one of the following properties:.

More preferably, the component (A), in particular the propylene homopolymer, is endowed with all the properties above.

Polyolefins suitable for use as component (A) are available on the market and can be obtained by polymerizing the relevant monomers in the presence a catalyst selected from metallocene compounds, highly stereospecific Ziegler-Natta catalyst systems and combinations thereof.

Preferably, the polymerization processes to prepare the component (A) is carried out in the presence of a highly stereospecific Ziegler-Natta catalyst system comprising:.

The solid catalyst component (<NUM>) preferably comprises TiCl<NUM> in an amount securing the presence of from <NUM> to <NUM>% by weight of Ti with respect to the total weight of the solid catalyst component (<NUM>).

The solid catalyst component (<NUM>) comprises at least one stereoregulating internal electron donor compound selected from mono or bidentate organic Lewis bases, preferably selected from esters, ketones, amines, amides, carbamates, carbonates, ethers, nitriles, alkoxysilanes and combinations thereof.

Preferred donors are the esters of phthalic acids such as those described in <CIT> and <CIT>, in particular di-isobutyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzylbutyl phthalate and combinations thereof.

Esters of aliphatic acids can be selected from esters of malonic acids such as those described in <CIT>, <CIT>, <CIT>, esters of glutaric acids such as those disclosed in <CIT>, and esters of succinic acids such as those disclosed <CIT>.

Particular type of diesters are those deriving from esterification of aliphatic or aromatic diols such as those described in <CIT> and <CIT>.

In some embodiments, the internal donor is selected from <NUM>,<NUM>-diethers such as those described in <CIT>, <CIT> and <CIT>.

Specific mixtures of internal donors, in particular of aliphatic or aromatic mono or dicarboxylic acid esters and <NUM>,<NUM>-diethers as disclosed in <CIT> and <CIT> can be used as internal donor.

Preferred magnesium halide support is magnesium dihalide.

The amount of internal donor that remains fixed on the solid catalyst component (<NUM>) is <NUM> to <NUM>% by moles, with respect to the magnesium dihalide.

Preferred methods for the preparation of the solid catalyst component (<NUM>) are described in <CIT>.

The preparation of catalyst components according to a general method is described for example in European Patent Applications <CIT>, <CIT>, <CIT> and <CIT>.

In some embodiments, the catalyst system comprises an Al-containing cocatalyst (<NUM>) selected from Al-trialkyls, preferably selected from the group consisting of Al-triethyl, Al-triisobutyl and Al-tri-n-butyl. The Al/Ti weight ratio in the catalyst system is from <NUM> to <NUM>, preferably from <NUM> to <NUM>.

In embodiments, the catalyst system comprises a further electron donor compound (<NUM>) (external electron donor) selected among silicon compounds, ethers, esters, amines, heterocyclic compounds, particularly <NUM>,<NUM>,<NUM>,<NUM>-tetramethylpiperidine, and ketones.

Preferred silicon compounds are selected among methylcyclohexyldimethoxysilane (C-donor), dicyclopentyldimethoxysilane (D-donor) and mixtures thereof.

The polymerization, which can be continuous or batch, is carried out in at least one polymerization stage in liquid phase or in gas phase.

The liquid-phase polymerization can be either in slurry, solution or bulk (liquid monomer). This latter technology is the most preferred and can be carried out in various types of reactors such as continuous stirred tank reactors, loop reactors or plug-flow reactors.

The gas-phase polymerization stages can be carried out in gas-phase reactors, such as fluidized or stirred, fixed bed reactors or a multizone reactor as illustrated in <CIT>.

The reaction temperature is comprised in the range from <NUM> to <NUM> and the polymerization pressure is from <NUM> to <NUM> MPa for a process in liquid phase and from <NUM> to <NUM> MPa for a process in the gas phase.

The molecular weight of the propylene copolymers obtained in the polymerization stages is regulated using chain transfer agents, such as hydrogen or ZnEt<NUM>.

In one embodiment, the component (B) is a low molecular weight compound having a polar group, the compound being preferably selected from aminosilanes, epoxysilanes, amidosilanes, acrylosilanes and mixtures thereof, preferably an aminosilane.

In a preferred embodiment, the component (B) comprised in the film or sheet according to the present disclosure is a modified polymer functionalized with polar compounds and, optionally, with a low molecular weight compound having a reactive polar group. Preferably, the modified polymer is an olefin polymer, preferably selected from polyethylenes, polypropylenes and mixtures thereof.

Polypropylenes are preferably selected from propylene homopolymers, propylene copolymers with at least one alpha-olefin of formula CH<NUM>=CHR, where R is H or a linear or branched C2-C8 alkyl, and mixtures thereof.

Polyethylenes are preferably selected from HDPE, MDPE, LDPE, LLDPE and mixtures thereof.

The modified olefin polymers are selected from graft copolymers, block copolymers and mixtures thereof.

Preferably, the modified polymers are functionalized with groups derived from polar compounds, including but not limited to acid anhydrides, carboxylic acids, carboxylic acid derivatives, primary and secondary amines, hydroxyl compounds, oxazoline, epoxides, ionic compounds and combinations thereof. Specific examples of said polar compounds are unsaturated cyclic anhydrides, their aliphatic diesters, and diacid derivatives.

Preferably, the component (B) is a polyolefin, preferably selected from polyethylenes, polypropylenes and mixtures thereof, functionalized with a compound selected from the group consisting of maleic anhydride, C1-C10 linear or branched dialkyl maleates, C1-C10 linear or branched dialkyl fumarates, itaconic anhydride, C1-C10 linear or branched itaconic acid, dialkyl esters, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

In a preferred embodiment, the component (B) is a polyethylene and/or a polypropylene grafted with maleic anhydride (MAH-g-PP and/or MAH-g-PE).

In a further preferred embodiment, the component (B) is a polyethylene and/or a polypropylene grafted with maleic anhydride, having at least one of the following properties:.

In a preferred embodiment, the polyethylene and/or a polypropylene grafted with maleic anhydride has all the properties above.

Modified polymers are known in the art and can be produced by functionalization processes carried out in solution, in the solid state or preferably in the molten state, eg. by reactive extrusion of the polymer in the presence of the grafting compound and of a free radical initiator. Functionalization of polypropylene and/or polyethylene with maleic anhydride is described for instance in <CIT>.

Examples of modified polyolefin suitable for use as component (B) are the commercial products Amplify™ TY by The Dow Chemical Company, Exxelor™ by ExxonMobil Chemical Company, Scona® TPPP by Byk (Altana Group), Bondyram® by Polyram Group and Polybond® by Chemtura and combinations thereof.

Amino resins are resins formed by condensation polymerization of compounds containing an amino group and formaldehyde. Preferably, the component (C) is an amino resin containing an amino group selected from primary aliphatic amine, secondary aliphatic amine, cycloaliphatic amine, aromatic amine, polyamines, urea, urea derivatives and mixtures thereof.

More preferably, the component (C) is selected from the group consisting of urea-formaldehyde resins, melamine-formaldehyde resins, melamine-urea copolymer resins and mixtures thereof; even more preferably component (C) is a melamine-formaldehyde resin. Melamine-formaldehyde resins includes modified melamine-formaldehyde resins, such as ether-modified melamine formaldehyde resins.

Preferably, the solubility in water at <NUM> of the amino resin, more preferably of the melamine-formaldehyde resin, is equal to or greater than <NUM>% by weight, more preferably equal to or higher than <NUM>% by weight, more preferably equal to or higher than <NUM>% by weight. In one embodiment, the upper limit of the solubility in water is <NUM>% by weight for each lower limit.

The amino resins suitable for use as component (C) are known in the art and obtainable by known condensation processes of the relevant monomers. They are also commercial products present on the market with the tradenames Saduren® marketed by BASF, Maprenal® marketed by Prefere Resins Holding GmbH and Hiperesin marketed by Chemisol Italia Srl.

The component (D) is optionally but preferably present in the polymer blend, and it is preferably selected from the group consisting of antistatic agents, anti-oxidants, slipping agents anti-acids, melt stabilizers, nucleating agents and combinations thereof, of the type used in the polyolefin field.

The amount of component (D) refers to the total amount of the additives comprised in the mixture.

Preferably, the polymer blend is obtained/obtainable by melt blending a mixture comprising:.

In one embodiment, the polymer blend is obtained/obtainable by melt blending a mixture consisting of components (A), (B), (C) and optionally (D) in the amounts indicated above; preferably the mixture consists of components (A), (B), (C) and (D).

In one embodiment, the film or sheet comprises a polymer blend obtained/obtainable by melt blending a mixture further comprising (E) up to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, of an inorganic filler, the amount of (E) being referred to the total weight of (A)+(B)+(C)+(D)+(E), the total weight being <NUM>%.

The inorganic filler is preferably selected from the group consisting of minerals, such as talc and silico-aluminates, glass fibers, glass beads, carbon fibers, natural fibers and mixtures thereof.

In one embodiment, the polymer blend has MFR(TOT) measured according to the method ISO <NUM>-<NUM>:<NUM> (<NUM>/<NUM>) of less than <NUM>/<NUM>. , preferably from <NUM> to <NUM>/<NUM>. , more preferably from <NUM> to <NUM>/<NUM>.

The melt blending preferably comprises extruding the components (A), (B), (C), and optionally (D) and/or (E), into an extruder operated at a temperature higher than the melting temperature of component (A).

More preferably, the melt blending process comprises the steps of:.

In step (i), the components (A), (B), (C), and optionally (D) and/or (E), are metered to the extruder simultaneously, optionally pre-mixed in the dry state, or sequentially in any order.

Preferably, in step (ii) the components (A), (B), (C), and optionally (D) and/or (E), are heated to a temperature of from <NUM> to <NUM>, preferably of from <NUM> to <NUM>. Preferably, the temperature referred to is the temperature of the head zone of the extruder.

The step (iii) preferably comprises pelletizing the molten polymer blend or forming the molten polymer blend into a film or sheet.

In pelletizing, the extrudate exiting the die is cooled to solidification and subsequently cut into pellets or, alternatively, the molten extrudate is cut into pellets as it emerges from the die and the pellets are subsequently cooled. Cutting and cooling can be carried out in water and/or in air.

Alternatively, the molten polymer blend is formed into a film or sheet by cast film/sheet extrusion or blown film/sheet extrusion. In cast film extrusion, the molten polymer blend (extrudate) exiting a linear slit die is cooled to the solid state by contact with chill rolls and wound onto reels. In blown film extrusion, the molten polymer blend (extrudate) exiting an annular die as a tube is cooled by air supplied from the inside of the tube. The inflated air also prevents the film from collapsing.

According to an embodiment, in step (iii) the molten polymer blend is formed into a film or sheet and the melt blending process comprises an additional step (iv) of stretching (orienting) the film or sheet in at least one direction, preferably in two directions (machine and transverse direction). Stretching of the film or sheet in two directions is carried out sequentially, eg. using a tenter frame, or simultaneously, eg. using either a tenter frame or a tubular process.

In one embodiment, the film or sheet for use according to the present disclosure is obtained/obtainable by feeding the pelletized polyolefin blend to an extruder, preferably to a twin screw extruder, remelting the pelletized polyolefin blend and extruding the remolten polyolefin blend through a die, preferably by cast film/sheet extrusion or blown film/sheet extrusion.

The remelting temperature is preferably from <NUM> to <NUM>, more preferably of from <NUM> to <NUM>.

In one embodiment, the film or sheet for use according to the present disclosure is a monolayer film or sheet comprising or consisting essentially of or consisting of the polyolefin blend as described above. In one embodiment, the monolayer film or sheet comprises the polyolefin blend. In a further embodiment, the monolayer film or sheet consists of the polyolefin blend.

In one preferred embodiment, the film or sheet for use according to the present disclosure is a monolayer film having thickness of from <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, especially <NUM> to <NUM>.

In an alternative embodiment, the film or sheet for use according to the present disclosure is a multilayer article comprising a top layer and a base layer, the top layer comprising or consisting of the polyolefin blend as described above and the base layer comprising or consisting of a material selected from the group consisting of metals, polymers, ceramic, glass and combinations thereof. In one embodiment, the top layer consists of the polyolefin blend as described above and the base layer consists of a material selected from the group consisting of metals, polymers, ceramic, glass and combinations thereof.

In one embodiment, the film or sheet for use according to the present disclosure is a two-layer article consisting of a top layer and a base layer, the top layer comprising or consisting of the polyolefin blend as described above and the base layer comprising or consisting of a material selected from the group consisting of metals, polymers, ceramic, glass and combinations thereof.

In one embodiment, the two-layer article consists of a top layer and a base layer, wherein the top layer consists of the polymer blend as described above and the base layer consists of a material selected from the group consisting of metals, polymers, ceramic, glass and combinations thereof.

In one embodiment, the film or sheet for use according to the present disclosure is a multilayer article, preferably a two-layer article, comprising a top layer and a base layer, wherein the top layer comprises or consists of the polyolefin blend as described above and has thickness of from <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM> to <NUM>, especially <NUM> to <NUM> and the base layer comprises or consists of a material selected from the group consisting of metals, polymers, ceramic, glass and combinations thereof and has thickness of from <NUM> to <NUM>, preferably from <NUM> to <NUM>, depending on the material.

In one embodiment, the multilayer article comprises at least one additional layer, such as a reinforcing layer adhered to the surface of the base layer opposite to the surface onto which the top layer is arranged and/or at least one intermediate layer interposed between the top layer and the base layer.

In the embodiments above, the base layer preferably comprises a thermoplastic polyolefin selected from polyethylene, polypropylene, polybutene-<NUM>, polyvinyl chloride, polyether, polyketone, polyetherketone, polyester, polyacrylate, polymethacrylate, polyamide, polycarbonate, polyurethane, polythiophenylene, polybutene terephthalate, polystyrene and mixtures thereof.

Thermoplastic polymers suitable for use in the base layer are known in the art and are available on the market. Preferably, the polyolefin is selected from polypropylene, polyethylene, polybutene-<NUM> and mixtures thereof. More preferably, the polyolefin is a propylene polymer selected from the group consisting of propylene homopolymers, propylene copolymers with at least one alpha-olefin of formula CH<NUM>=CHR, where R is H or a linear or branched C2-C8 alkyl and mixtures thereof.

The propylene copolymer is a random propylene copolymer preferably comprising <NUM>-<NUM>% by weight of the at least one alpha-olefin or an heterophasic propylene polymer comprising a matrix and a dispersed elastomeric phase, wherein the matrix comprises a propylene homopolymer, a random propylene copolymer comprising <NUM>-<NUM>% by weight of a at least one alpha-olefin of formula CH<NUM>=CHR, where R is H or a linear or branched C2-C8 alkyl and mixtures thereof, and the dispersed phase comprises a propylene copolymer comprising <NUM>-<NUM>% by weight of monomer units deriving from at least one alpha-olefin of formula CH<NUM>=CHR, where R is H or a linear or branched C2-C8 alkyl and mixtures thereof.

The alpha-olefin is preferably selected from ethylene, butene-<NUM>, hexene-<NUM>, <NUM>-methy-pentene-<NUM>, octene-<NUM> and combinations thereof, ethylene being the most preferred.

The thermoplastic polyolefin of the base layer optionally comprises up to <NUM>% by weight, based on the weight of the base layer, preferably <NUM>-<NUM>% by weight, of an additive selected from the group consisting of fillers, pigments, dyes, extension oils, flame retardants (e. aluminum trihydrate), UV resistants (e. titanium dioxide), UV stabilizers, lubricants (e. , oleamide), antiblocking agents, slip agents, waxes, coupling agents for fillers, and combinations thereof, the additive being known in the polymer compounding art.

In one embodiment, the base layer comprises or consists of a thermoplastic polyolefin, preferably a propylene polymer, and up to <NUM>% by weight, preferably <NUM>-<NUM>% by weight, more preferably <NUM>-<NUM>% by weight, based on the weight of the base layer, of a mineral filler, more preferably of talc. In one embodiment, the base layer consists of the thermoplastic polymer, preferably of the polyolefin described above. In an embodiment the base layer consists of the thermoplastic polymer, preferably of the polyolefin described above, and the additive.

In the embodiments above, the metal of the base layer is preferably selected from the group consisting of aluminum, copper, iron, steel, titanium, lithium, gold, silver, manganese, platinum, palladium, nickel, cobalt, tin, vanadium, chromium, alloys comprising at least one of said metals (eg. brass), and combinations thereof; more preferably, the base layer comprises or consists of aluminum, particularly preferably the base layer consists of aluminum.

The base layer is preferably in the form of a film, sheet, woven or nonwoven fabric, web or foam, depending on the material.

In one embodiment, the film or sheet for use according to the present disclosure is a two-layer article consisting of a top layer and a base layer, wherein the top layer consists of the polymer blend and the base layer consists of a metal as described above. In this embodiment, the top layer and the base layer preferably have the thickness as described above.

In a particularly preferred embodiment, the film or sheet is a two-layer article consisting of top layer and a base layer, wherein the top layer comprises the polyolefin blend as described above and has thickness of from <NUM> to <NUM>, preferably from <NUM> to <NUM>, and the base layer consists of an aluminum film having thickness of from <NUM> to <NUM>, preferably from <NUM> to <NUM>. The handling of the film of this embodiment is improved.

The process to produce the multilayer article is preferably selected from coextrusion, lamination, extrusion lamination, extrusion coating, compression molding, back injection molding, back foaming, back compression molding and combinations thereof, depending on the material of the back layer.

In coextrusion, the multilayer article is formed by cooling an extrudate comprising superimposed melt streams, wherein a first melt stream comprises or consists of the material of the top layer and a second melt stream comprises or consists of the material of base layer, (eg. a thermoplastic or a thermoset polymer).

In lamination, the base layer, eg. a thermoplastic polymer, and the top layer are made to adhere using heated compression rollers.

In extrusion lamination, the top layer and the base layer are laminated with heated compression rollers and, during lamination, a molten polymer is extruded between said layers acting as bonding layer.

In extrusion coating, a molten stream comprising or consisting of the material of the top layer is extruded through an horizontal die and applied onto the moving base layer.

In compression molding, the base layer and the top layer are superimposed and made to adhere and, optionally but preferably shaped, by putting the superimposed films into an open heated cavity of a mold, closing the mold with a plug member and applying pressure.

In back injection molding, the base layer is introduced into an injection mold, the mold is closed and a molten stream comprising or consisting of the polymer blend of the top layer is injected into the mold at a temperature of from <NUM> to <NUM> and a pressure of from <NUM> to <NUM> MPa, thereby forming the top layer and bonding the top layer to the base layer. When the base layer comprises or consists of a thermoplastic polymer, the top layer is introduced into an injection mold, the mold is closed and a molten stream comprising or consisting of the material of the base layer is injected into the mold and bonded to the top layer.

The use of the film or sheet as printing plate in an extrusion-based additive manufacturing process comprises selectively depositing a molten thermoplastic material (P) on a film or sheet according to the present disclosure with a 3D printing device.

Therefore, in a further aspect the present disclosure refers to an extrusion-based additive manufacturing process comprising a step of selectively depositing a molten thermoplastic material (P) on a printing plate comprising the film or sheet according to the present disclosure.

The extrusion-based additive manufacturing process preferably comprises the steps of:.

Before placing the film or sheet of the present disclosure on the printing platform of a 3D printing device, the film or sheet is optionally but preferably cut into pieces of the appropriate dimensions.

The step (i) comprises laying the film or sheet on the printing platform or releasably fixing the film or sheet to the printing platform or coating the printing platform with a continuous layer comprising or consisting of the film or sheet.

Printing platforms of 3D printers are generally made of metal or glass and the film or sheet of the present disclosure may be displaced during printing. Since the stability of the printing surface is of the uttermost importance in a 3D printing process, in a preferred embodiment, the step (i) comprises releasably fixing the film or sheet to the printing platform of the 3D printing device.

Preferably, the film or sheet is releasably fixed to the printing platform by gluing the film or sheet to the printing plate with a releasable adhesive, by vacuum, mechanical or magnetic clamping or by combinations thereof, depending on the material of the printing platform and on the material of the base layer, if present in the film or sheet.

In a preferred embodiment, the step (i) comprises vacuum-clamping the film or sheet of the present disclosure to the printing platform. A vacuum clamping printing platform comprises a vacuum chamber connected to the surface of the platform by holes of variable bore, spacing and geometry. By applying vacuum to the chamber, the film or sheet is retained on the surface of the printing platform. The vacuum ensures that the film or sheet is flat, wrinkle-free and positionally stable during printing.

In one further embodiment, the step (i) comprises coating the printing platform with a continuous layer of the polymer blend as described above, thereby forming a film or sheet. Preferably, the coating is realized by an extrusion-based additive manufacturing process.

Thus, in a further aspect, the present disclosure refers to the use of the polymer blend as described above as printing material (P) in an extrusion-based additive manufacturing process.

Optionally but preferably, the step (i) further comprises heating the printing platform, especially the vacuum-clamping printing platform, to a temperature up to <NUM>, preferably up to <NUM>. In one embodiment, the lower limit for the heating temperature is of <NUM> for each upper limit.

The thermoplastic material (P) of step (ii) is preferably selected from the group consisting of polyolefins, polylactic acid (PLA), polyamides (PA) comprising among others PA6 and PA6,<NUM>, polycarbonates (PC), polyurethanes (TPU), polyesters comprising among others polyethylene terephthalates (PET), glycol-modified polyethylene terephthalates (PETG), polyhydroxy butyrate (PHB), polyetherketones comprising among others polyetherketoneketone (PEKK), polyetheretherketone (PEEK), polyacrylates, polymethacrylates, poly(methyl methacrylate), polythiophenylene, acrylonitrile-butadiene-styrene polymers (ABS), acrylonitrile-styrene-acrylate polymers (ASA), the polymer blend as described above, and combinations thereof.

Preferably, the thermoplastic material (P) comprises a propylene polymer and/or an ethylene polymer.

In a preferred embodiment, the thermoplastic material (P) is a polyolefin composition selected from the group consisting of:.

The polyethylene composition (I) is a multimodal polyethylene composition described in detail in the international patent application <CIT>, herein incorporated by reference in its entirety.

The heterophasic polypropylene composition (II) optionally comprises up to <NUM> % by weight of an inorganic filler c2) and up to <NUM>% by weight of a compatibilizer d2).

The inorganic filler c2) of the composition (II) and the inorganic filler e3) of the composition (III) are preferably independently selected from the group consisting of talc, mica, calcium carbonate, wollastonite, glass, especially glass fibers and glass spheres, carbon and combinations thereof.

The compatibilizer d2) is preferably a polyethylene and/or a polypropylene grafted with maleic anhydride (MAH-g-PP and/or MAH-g-PE).

The heterophasic composition (II) is described in detail in the international patent application <CIT>, herein incorporated by reference in its entirety.

The polypropylene composition (III) is described in detail in the international patent application <CIT>, herein incorporated by reference in its entirety.

The thermoplastic material (P) is fed to the 3D printing device in the form of a filament (filament-based 3D printing process) or of a pellet (pellet-based 3D printing process).

In embodiments, the printing temperature of the thermoplastic polymer (P) in step (ii) is up to <NUM>, eg. for PEEK, and depends on the chemical nature of the polymer. The printing temperatures of polyolefins is from <NUM> to <NUM>.

In one embodiment, the 3D printed article is not removed from the printing plate, eg. for aesthetic reasons, i.e. the optional step (iii) is not present. In this embodiment, the step (ii) further comprises the step of removing the 3D printed article and the printing plate from the printing platform of the printing device (eg. by interrupting the vacuum).

In an alternative embodiment, the optional step (iii) comprises removing the 3D printed article and the printing plate from the printing platform of the printing device (eg. by interrupting the vacuum) and subsequently removing the printing plate from the 3D printed article.

Alternatively, the step (iii) comprises removing the 3D printed article from the printing plate while retaining the printing plate on the printing platform.

The 3D printing plate comprising the film or sheet of the present disclosure has proven to be versatile since it allows secure 3D-printing and easy removal of several thermoplastic printing materials.

In further aspect, the present disclosure refers to a 3D printing kit comprising:.

Preferably, the component (K1) of the 3D printing kit comprises a thermoplastic polymer (P) as described above, particularly preferably a polyolefin composition selected from the group consisting of the polyolefin composition (I), (II), (III) and (IV) as described above.

The features describing the subject matter of the present disclosure are not inextricably linked to each other. As a consequence, a certain level of preference of one feature does not necessarily involve the same level of preference of the remaining features of the same or different components. It is intended in the present disclosure that any preferred range of features of components from (A) to (D) from which the polyolefin blend is obtained can be combined independently from the level of preference, and that components from (A) to (D) can be combined with any possible additional component, and its features, described in the present disclosure.

The following examples are illustrative only, and are not intended to limit the scope of the disclosure in any manner whatsoever.

The following methods are used to determine the properties indicated in the description, claims and examples.

Melt Flow Rate: Determined according to the method ISO <NUM> (<NUM>, <NUM> for the thermoplastic polyolefins; <NUM>/<NUM> for the compatibilizer).

Solubility in xylene at <NUM>: <NUM> of polymer sample and <NUM> of xylene are introduced in a glass flask equipped with a refrigerator and a magnetic stirrer. The temperature is raised in <NUM> minutes up to <NUM>. The obtained clear solution is kept under reflux and stirring for further <NUM> minutes. The solution is cooled in two stages. In the first stage, the temperature is lowered to <NUM> in air for <NUM> to <NUM> minute under stirring. In the second stage, the flask is transferred to a thermostatically controlled water bath at <NUM> for <NUM> minutes. The temperature is lowered to <NUM> without stirring during the first <NUM> minutes and maintained at <NUM> with stirring for the last <NUM> minutes. The formed solid is filtered on quick filtering paper (eg. Whatman filtering paper grade <NUM> or <NUM>). <NUM> of the filtered solution (S1) is poured in a previously weighed aluminum container, which is heated to <NUM> on a heating plate under nitrogen flow, to remove the solvent by evaporation. The container is then kept on an oven at <NUM> under vacuum until constant weight is reached. The amount of polymer soluble in xylene at <NUM> is then calculated. XS(I) and XSA values are experimentally determined. The fraction of component (B) soluble in xylene at <NUM> (XSB) can be calculated from the formula: <MAT> wherein W(A) and W(B) are the relative amounts of components (A) and (B), respectively, and W(A)+ W(B)=<NUM>.

C2 content in propylene-ethylene copolymer (II): <NUM>C NMR spectra were acquired on a Bruker AV-<NUM> spectrometer equipped with cryoprobe, operating at <NUM> in the Fourier transform mode at <NUM>. The peak of the Pββ carbon (nomenclature according to <NPL>)) was used as internal reference at <NUM> ppm. The samples were dissolved in <NUM>,<NUM>,<NUM>,<NUM>-tetrachloroethane-d2 at <NUM> with a <NUM> % wt/v concentration. Each spectrum was acquired with a <NUM>° pulse, <NUM> seconds of delay between pulses and CPD to remove <NUM>H-<NUM>C coupling. <NUM> transients were stored in <NUM> data points using a spectral window of <NUM>. The assignments of the spectra, the evaluation of triad distribution and the composition were made according to Kakugo [<NPL>)]. Owing to the low amount of Propylene inserted as regioirregular units, ethylene content was calculated according to Kakugo [<NPL>)] using only triad sequences with P inserted as regular unit. <MAT> <MAT><MAT><MAT><MAT><MAT>.

Where S = Tββ + Tβδ + Tδδ + Sββ + Sβδ + <NUM>γδ + <NUM>δδ.

Tensile Modulus: Determined according to the method ISO <NUM>-<NUM>,-<NUM>:<NUM>.

Peel test: the peel resistance Rpeel of 3D printed test specimens (<NUM> x <NUM> x <NUM>) on the printing plate was determined according to DIN EN <NUM> using the test machine ZWICK Z005 with a load cell of <NUM> kN. The 3D printed test specimen was separated from the printing plate along the longest axis by means of a blade, starting from one side over a length of <NUM>. The separated part of the 3D printed test specimens was clamped to the testing machine at an angle of <NUM>° with respect to the printing plate and peeled with a speed of <NUM>/min. For each 3D printed test specimen, the measurements were performed at the a temperature corresponding to the temperature T(p) of the printing plate, straightly after the printing process. A load cell was used to continuously measure the force required to peel off the test specimens from the printing plate. From the plateau (traverse travel between approximately <NUM> and <NUM>) the peel force Fpeel was determined by arithmetically averaging the measured tensile forces in the plateau. The peel resistance Rpeel was calculated according to the formula: <MAT> wherein b is the width of the test specimens (<NUM>). Five test specimens were used for each combination 3D printing material/printing plate. The mean value of the Rpeel over five measurements is used as Rpeel value of the test specimen.

Moplen HF501N, a propylene homopolymer from LyondellBasell, having a melt flow rate of <NUM>/<NUM>. (ISO1133; <NUM>/<NUM>) and tensile modulus (ISO <NUM>-<NUM>,-<NUM>:<NUM>) of <NUM> MPa.

Amplify TY <NUM> marketed by The Dow Chemical Company, a maleic anhydride (MAH) grafted polymer concentrate with MAH grafting level of <NUM>-<NUM> wt. %, MFR of <NUM>/<NUM>. (ISO1133; <NUM>/<NUM>) and melting temperature of <NUM> measured by DSC.

Hiperesin MF 100C a melamine-formaldehyde powder resin obtained from Chemisol Italia having solubility in water in the range <NUM>-<NUM> wt.

Irganox® <NUM> marketed by BASF, is <NUM>,<NUM>-bis[<NUM>-[,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-hydroxyphenyl]-<NUM>-oxopropoxy]methyl]-<NUM>,<NUM>-propanediyl-<NUM>,<NUM>-bis(<NUM>,<NUM>-dimethylethyl)-<NUM>-hydroxybenzene-propanoate.

Irgafos® <NUM> marketed by BASF is tris(<NUM>,<NUM>-di-tert. -butylphenyl)phosphite.

The thermoplastic polymer filaments used in 3D printing tests are listed in Table <NUM>.

Ultimaker products are marketed by Ultimaker, Nederlands; Ultrafuse is a product marketed by BASF.

HECO1 is a polypropylene compound obtained by melt blending <NUM> wt. % of Moplen® 2000HEXP, an heterophasic propylene polymer marketed by LyondellBasell, with <NUM> wt. % of glass fibers (ThermoFlow <NUM> EC13 <NUM>) and <NUM> wt. % of additives.

Hifax® TYC 459P C1V301 is a <NUM> wt. % talc filled commercial propylene polymer composition sold by LyondellBasell, having MFR (<NUM>/<NUM>) of <NUM>/<NUM>. measured according to ISO <NUM>-<NUM>, flexural modulus (<NUM>, Tech A) of <NUM> MPa measured according to ISO <NUM>/A1 and Charpy impact strength - Notched of <NUM> kJ/m<NUM> at <NUM> and of <NUM> kJ/m<NUM> at -<NUM> measured according to ISO <NUM>-<NUM>/1eA.

Hostalen® GC7260, marketed by LyondellBasell, is an HDPE having Melt Flow Rate (<NUM>/<NUM>, ISO1133-<NUM>) of <NUM>/<NUM> and a melting temperature in the range <NUM>-<NUM>.

A mixture having the following composition:.

was fed to a twin-screw extruder ZSK-<NUM> (Coperion GmbH, Stuttgart, Germany), operating with a throughput of <NUM>/h at <NUM>. The melt was pelletized through a die plate having <NUM> holes of <NUM> diameter resulting in granules of a polymer blend. The granules of polymer blend were fed to a blown film line (HOSOKAWA ALPINE AG. , Augsburg, Germany) equipped with a <NUM> diameter single screw extruder and blown into a film employing a throughput of <NUM>/h and a temperature of <NUM> in the head zone of the extruder. The extruded bubbles had a diameter of <NUM>. The bubbles were cut and the resulting films having a thickness of <NUM> was wound onto a roll. For use as printing plate, the film was cut into pieces of <NUM> x <NUM>.

The film IP1 was laminated to an aluminum foil DPxx (anodized open pored) <NUM> thick, obtained from Alanod GmbH & Co. KG, Germany. The lamination was carried out continuously using a laminator UVL PRO <NUM> from Fetzel Maschinenbau GmbH, Germany with silicone rollers LA60ACO. <NUM> at <NUM> and <NUM> bar/(m<NUM>) surface pressure. The intake speed was <NUM>/min. For use as printing plate, the laminate was cut into pieces of size <NUM> x <NUM>.

The 3D printed test specimens (<NUM> x <NUM> x <NUM>) were produced with an Ultimaker <NUM>+ FFF printer using <NUM>% linear infill with ± <NUM>° angle relative to the longest axis of the specimens, a nozzle of <NUM> diameter, a line width of <NUM>, and a printing speed of <NUM>/s.

The printing plates were vacuum-clamped onto the printing platform of the printer and <NUM> layers each <NUM> thick were printed superimposed, leading to a test specimen <NUM> thick. All test specimens were printed without raft or brim. The nozzle printing temperature (T(n)) and temperature of the printing platform (T(p)) were set according to the specifications of the manufactures to avoid degradation of the printing materials.

Once the printing process was finished, the vacuum was switched off and the 3D printed articles were removed from the printing platform together with the printing plate.

The peel test was carried out immediately after the 3D printed article with the printing plate was removed from the platform.

For each combination of printing material/IP/printing temperature five specimens were printed consecutively and tested.

In examples E1-E10 the film IP1 was used as printing plate with the printing materials from PM1 to PM10. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In examples E11-E20 the film IP2 was used as printing plate with the printing materials from PM1 to PM10. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In examples E1-E10 the film IP2 was used as printing plate with the printing materials from PM1 to PM10. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In comparative examples CE31-CE40 the printing platform CP1 was used, in which a Ultimaker <NUM>+ glass bed from Ultimaker, Netherlands, was covered with 3DLac adhesive spray for 3D printers obtained from 3DLac, Spain. The same materials from PM1 to PM10 were used for printing. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In comparative examples CE41-CE50 the printing platform CP2 was used, in which an Ultimaker adhesion sheet from Ultimaker, Netherlands, was applied on an Ultimaker <NUM>+ glass bed. The same printing materials from PM1 to PM10 were used for printing. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In comparative examples CE51-CE60 the printing platform CP3 was used, in which a reinforced adhesive tape from <NUM>, USA (Scotch Filament Tape <NUM>), was applied on a Ultimaker <NUM>+ glass bed. The same materials from PM1 to PM10 were used for printing. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In comparative examples CE61-CE70 the printing platform CP4 was used, a polypropylene plate with a thickness of <NUM> from Technoplast GmbH, Germany. The same printing materials from PM1 to PM10 were used for printing. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

In comparative examples CE71-CE80 the printing platform CP5 was used, a polyethylene plate with a thickness of <NUM> from Technoplast GmbH, Germany. The same printing materials from PM1 to PM10 were used for printing. The nozzle temperature T(n) and the temperature of the printing platform T(p) used in each test are reported in Table <NUM>.

The peel resistance values (Rpeel [N/mm] with standard deviation) obtained the peel tests are reported in Tables <NUM> and <NUM>.

The printing plate of the present disclosure (IP1 and IP2) show adhesion to all investigated thermoplastic polymers in extrusion-based 3D printing, regardless of the polarity of the printing material. In particular, IP1 and IP2 show good adhesion to polyethylene and polypropylene, in contrast to conventional printing platforms.

Claim 1:
Use of a film or sheet comprising a polymer blend obtained by melt blending a mixture comprising:
(A) <NUM>% to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, more preferably from <NUM>% to <NUM>% by weight, more preferably from <NUM>% to <NUM>% by weight, of a polyolefin;
(B) <NUM>% to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, more preferably from <NUM> to <NUM>% by weight, more preferably from <NUM>% to <NUM>% by weight, of at least one compatibilizer;
(C) <NUM>% to <NUM>% by weight, preferably from <NUM>% to <NUM>% by weight, more preferably from <NUM>% to <NUM>% by weight, more preferably from <NUM>% to <NUM>% by weight of an amino resin; and
(D) <NUM>% to <NUM>% by weight, preferably <NUM>% to <NUM>% by weight, more preferably <NUM>% to <NUM>% by weight, more preferably <NUM>% to <NUM> % by weight, of at least one additive,
wherein the amounts of (A), (B), (C) and (D) are based on the total weight of (A)+(B)+(C)+(D), the total weight being <NUM>%,
as printing plate in an extrusion-based additive manufacturing process.