EP4251687A1

EP4251687A1 - Article made from a heavy plastic material

Info

Publication number: EP4251687A1
Application number: EP21801896.8A
Authority: EP
Inventors: Julien DAHAN; Benoît SCHNELL
Original assignee: ETA SA Manufacture Horlogere Suisse
Current assignee: ETA SA Manufacture Horlogere Suisse
Priority date: 2020-11-24
Filing date: 2021-10-28
Publication date: 2023-10-04
Also published as: US20230416473A1; KR20230090345A; EP4001356A1; WO2022111936A1; JP2023550117A; CN116457404A

Abstract

The invention relates to an article made from a material comprising, by weight: a metal and/or ceramic filler present in a percentage greater than 50% and less than or equal to 85%, at least one polymer present in a percentage greater than or equal to 15% and less than or equal to 50%, optionally at least one coupling agent present in a percentage greater than or equal to 0% and less than 10%, characterised in that the polymer (4) is bonded to the filler (2) and optionally to the coupling agent (3) by one or more bonds chosen from a hydrogen bond, a coordinate bond and an ionic bond. The present invention also relates to a method for manufacturing this article by injection moulding or by 3D printing.

Description

ARTICLE MADE IN A HEAVY PLASTIC MATERIAL

Technical field of the invention

The present invention relates to an article, and for example to a watch component, made of a heavy plastic material and resistant to shocks.

The present invention also relates to a method of manufacturing such an article made of a heavy plastic.

Technology background

[0003] Many trim components, such as the casebands and bracelets, are made of plastic materials. These components can be made by molding processes, which has the advantage of being able to obtain various shapes without any reworking operation. These components in plastic material have the characteristic of having a density close to 1 and therefore of being light. This can be a disadvantage for the user wishing to wear a watch with a certain weight on the wrist.

[0004] To overcome this drawback, it has been proposed, for example in document EP 2482 142, to make watch components, whether movement or casing, in plastic materials loaded with a high density metal powder. such as tungsten powder. These components are made by an injection molding process which allows to keep the advantage of shaping in the mold without subsequent recovery while increasing the density.

[0005] These materials thus combine certain advantages of plastics, such as the ease of shaping by injection, with those of metals, such as density, cold feel and metallic appearance. [0006] It is however possible to observe in these materials a reduction in the breaking strength and in the elongation with respect to the host polymer matrix. This decrease is attributed to a lack of cohesion of the material due to the incorporation of the metal powder of micrometric size in chains of polymers of nanometric size. Thus, for a material comprising a metallic (or ceramic) filler, a polyolefin (polyethylene, polypropylene) as polymer and polyurethane as coupling agent, this drop in properties due to the lack of cohesion of the material is observed.

[0007] This reduction in mechanical properties will impact the shock absorption capacity of the material. This type of material is therefore not suitable for applications requiring shock resistance, such as in the watchmaking field for the production of casebands, etc.

Summary of the invention

[0008] The object of the present invention is to propose a new composition of heavy plastic material making it possible to improve the cohesion of the material and thereby the mechanical properties of the material.

The invention finds a particularly interesting application in the field of watchmaking; however, the invention is not limited to such an application.

To this end, the present invention provides an article made of a material comprising by weight for a total of 100%:

- a filler in a metallic and/or ceramic material having a density greater than or equal to 3 g/cm ³ , said filler being present in a percentage greater than 50% and less than or equal to 85%, - at least one polymer present in a percentage greater than or equal to 15% and less than or equal to 50%,

- optionally at least one coupling agent present in a percentage greater than or equal to 0% and less than 10%,

- optionally at least one reinforcement present in a percentage between 0 and 10%,

- optionally at least one pigment present in a percentage between 0 and 5%,

- optionally at least one diluent and/or plasticizer present in a percentage of between 0 and 5%.

According to the invention, the polymer is bonded to the filler and/or the coupling agent is bonded respectively to the filler and to the polymer, when the material comprises at least one coupling agent, by one or more of the bonds which are a hydrogen bond, a coordination bond or an ionic bond.

[0012] These bonds are established between the oxidized surface, and/or electronic vacancies present at the surface of the filler, and groups of the polymer and/or of the coupling agent. For this purpose, the polymer and/or the coupling agent carry, by way of example, one or more of the following groups: NH _X , OH, COC, C=O, COOH. These bonds linking the filler, the polymer and, where appropriate, the coupling agent make it possible to ensure good cohesion of the material. They have the characteristic of having an interaction energy which is typically less than 100 kJ/mol or even 50 kJ/mol, which makes it possible to break the bonds between molecules during the rise in temperature during the manufacturing process and by there itself to ensure better mixing and better cohesion of the material after cooling and reformation of the bonds. The material thus developed has sufficient rigidity with a Young's modulus greater than or equal to 2.5 GPa, sufficient elongation at break which is greater than or equal to 5% and a sufficient breaking load which is greater than or equal to equal to 30 MPa, for a watchmaking application. It also has good toughness and has a density of between 2 and 7 g/cm ³ .

Furthermore, the present invention relates to a process for manufacturing this material by molding, by injection or by 3D printing.

The method has the characteristic that the base material for the filler is in the form of a powder having a BET greater than or equal to 0.01 m ² /g, preferably 2 m ² /g, more preferably 5 m ² /g, so as to obtain a filler with a sufficiently reactive surface to form the hydrogen, ionic and/or coordination bonds with the polymer and/or the coupling agent if the latter is present. The reactive surface, whatever the type of ceramic (oxides, nitrides or carbides) or of metal (steel, tungsten, etc.), thus comprises hydroxides, oxides and/or electronic vacancies.

Other characteristics and advantages of the present invention will appear in the following description of a preferred embodiment, presented by way of non-limiting example with reference to the accompanying drawings.

Brief description of figures

[0017] Figure 1 shows a timepiece comprising a middle part made with the heavy plastic material according to the invention.

Figure 2 schematizes the interactions between the surface of the filler, the coupling agent and the polymer.

Figure 3 schematically illustrates the hydrogen bonds which are established between the filler, the coupling agent and the polymer. Detailed description of the invention

The present invention relates to an article made of a composite material comprising a plastic material and a metallic or ceramic material.

[0021] By way of example, the article can be a constituent element of watches, jewellery, bracelets, etc.

[0022] The article can also be a constituent element of a bezel, for example a frame, a branch, a pad.

[0023] In a non-limiting and non-exhaustive manner, the article according to the invention can also be a constituent element, or form the entirety, of a sports article, a kitchen article, an article or a musical instrument, an article of leather goods or haberdashery, an automobile or aeronautical component, a component for an electronic article (for example protective cover for a telephone, computer keyboard, keyboard keys for computer, headphones, ...), a writing article, etc....

[0024] Advantageously, the article is a component whose functionality requires a certain resistance to impacts and shocks.

[0025] In the particular field of watchmaking, this article may for example be a covering component such as a middle part, a back, a bezel, a pusher, a bracelet link, a dial, a hand, a dial indexes, etc.

By way of illustration, a caseband 1 made with the material according to the invention is shown in Figure 1.

According to another exemplary embodiment (not shown), the article according to the invention may be a component of the movement, such as for example a plate.

According to the invention, the article is made of a material comprising at least two components which are a filler, metallic and/or ceramic, and a polymer. Thus, the material can be qualified as a composite material.

[0029] Optionally, the material may comprise one or more coupling agents if the physico-chemical interaction between the filler and the polymer is not sufficient.

[0030] Optionally, the material may also comprise a reinforcement.

[0031] Optionally, the material may also comprise one or more pigments.

[0032] Optionally, the material may also include diluents and/or plasticizers.

The filler can be metallic and/or ceramic.

[0034] For the metallic material, it may be a conventional carbon steel, a stainless steel, copper, a copper alloy, titanium, a titanium alloy or even tungsten. . Preferably, it is a nickel-free stainless steel.

For the ceramic material, it may be carbides, nitrides or oxides such as ZrÛ2, Ce02, ZnO, etc.

It can also be a filler comprising a mixture of metallic and ceramic materials.

[0037] The filler as a whole is in the majority by mass but less than or equal to 85% by weight. It is therefore comprised by weight between 50 and 85% by weight (lower limit not included), for example between 50 and 75% or even between 50 and 65% (lower limit not included).

Preferably, it is comprised in a percentage by weight of between 60 and 80%, and even more preferably between 65 and According to the invention, the filler is introduced during the manufacturing process in the form of a powder with a high specific surface (> 0.01 m ² /g) which de facto, in the absence of specific treatment, will present on its surface from changes in its composition and/or defects, regardless of the type of metallic or ceramic filler. These may be oxides and hydroxides present on the oxidized surface of the powder and defects such as electronic vacancies, which will allow interaction via different bonds with the polymer and/or the coupling agent if this last is present. Figure 2 thus schematizes the interactions which are established between the surface of the filler 2, the coupling agent 3 and the polymer 4.

The material comprises one or more polymers capable of generating hydrogen, ionic and/or coordination bonds with the filler and/or the coupling agent when it is present. All these physico-chemical bonds have the characteristic of having a low interaction energy, typically between 5 and 100 kJ/mol, which makes it possible to break the bonds between molecules during the rise in temperature during the injection. or the 3D printing of the materials, these physico-chemical bonds being re-established during the cooling of the material after the injection or the 3D printing. This characteristic allows better mixing, better compatibility between the components and therefore better cohesion of the material at the molecular level and therefore better overall cohesion of the material.

The polymer or all of the polymers represents a percentage by weight of between 15 and 50% of the material (upper limit excluded), for example between 25 and 50% or even between 35 and 50% (upper limit excluded).

[0042] Preferably, the polymer or all the polymers represent a percentage by weight of between 20 and 40%, and more preferably between 25 and 35% of the material. To form a hydrogen bond, the polymer comprises a hydrogen bond donor comprising a group with a hydrogen atom, such as an NH or OH group, and a hydrogen bond acceptor comprising a group with a more electronegative atom such as hydrogen, such as nitrogen, oxygen or an atom from the halogen group such as fluorine, chlorine, bromine, etc. The hydrogen bond is established with the hydroxides and oxides present on the oxidized surface of the metallic or ceramic filler. By way of example, the hydroxide group at the surface of the filler interacts with a C=O, R-OH, COC, R-NHxR′ group of the polymer. Preferably, the hydrogen bond donor and acceptor are adjacent on the polymer chain. Still by way of example, the polymer may be a polyamide with the RC(=0)-NH-R' unit with therefore the C=0 group comprising the bond acceptor oxygen atom and the NH group comprising the Adjacent bond donor hydrogen atom.

The ionic bonds in the context of the invention result from the interaction between a negatively charged basic function and a positively charged acid function. The bond is established with transfer of an H ⁺ ion from an OH group at the surface of the metallic or ceramic filler towards the polymer. By way of example, the polymer may contain an NH _X group and more specifically be a polyamine, with R—NH _x+i -R′+/MO— being obtained after the acid-base reaction.

[0045] Coordination bonds are a special type of covalent bond where the common electron pair only comes from one of the bonded atoms as opposed to the conventional covalent bond where one electron comes from each of the bonded atoms. According to the invention, this bond involves more specifically a Lewis base formed by the polymer, associated with an electronic vacancy at the surface of the charge forming the Lewis acid. Any polymer carrying a function comprising an atom bearing non-binding doublets can share this doublet to "stabilize" the electronic gap. It may for example be the non-binding doublet of nitrogen or oxygen in R(C=0)NR', in R0(C=0)NR' and in R(C=0)0R'. The polymer can also carry amine (NHx) or carboxylic acid (COOH) functions capable of forming this bond with an electronic gap at the surface of the charge. Mention may be made, for example, of polyurethanes and polyesters.

The material may comprise a coupling agent in a percentage of between 0% and less than 10%, advantageously between 0.1 and 10%, more advantageously between 0.1 and 5%, even more advantageously between 0.5 and 3%. The coupling agent is also capable of being linked to the filler and to the polymer by one or more bonds chosen from hydrogen, ionic and coordination bonds as described above. It will be specified that in the presence of a coupling agent, the bond is established respectively between the coupling agent and the filler and between the coupling agent and the polymer without necessarily direct bonds between the filler and the polymer. As for the polymer, the coupling agent can comprise at least one group chosen from C=O, COC, OH, NHx or even COOH. By way of example for hydrogen, ionic and coordination bonds, it may be polyurethane with the motif RO-C=0-NH-R'. Preferably, the coupling agent has a long chain with a minimum of 20 carbon atoms. Still by way of example for hydrogen, ionic and/or coordination bonds, it may be a hydroxysilane with an amide or amine function and advantageously at least 20 carbon atoms on the chain. Still by way of example, these may be ionic bonds with an acid-base reaction taking place during the manufacturing process between the filler and the coupling agent with transfer of an H ⁺ ion from an OH group in load area. They may also be ionic bonds between the coupling agent and the polymer comprising one or the other respectively of the carboxylic acid R-COOH and amine R'-NH _X functions forming the base with production of RCOO-/ R'-NH _x+i + after the acid-base reaction. Of alternatively, the polymer and the coupling agent can already be loaded before being brought together. In which case, for the example above, the coupling agent and the polymer respectively carry either the basic function RCOO-, or the acid function R′-NH _x+i +.

[0047] Optionally, the material may also comprise a reinforcement in a percentage by weight of between 0 and 10%, advantageously between 1 and 6%. The reinforcement can be present in different forms, for example, in the form of fibers or particles. For example, it can be glass fibers, glass beads, carbon fibers and/or aramid fibers with a fiber length less than or equal to 300 μm, and preferably 200 μm . The purpose of the reinforcement is to improve the toughness of the material, to limit the shrinkage of the material during injection and/or to improve the electrical conductivity of the material.

[0048] Optionally, the material may also comprise one or more pigments in a total percentage of between 0 and 5% by weight. The pigment can be an organic or inorganic pigment. For example, it can be carbon black for black, diketopyrrolopyrrole for red (e.g. Irgazin Red K3840LW from BASF), copper phthalocyanine for blue (e.g. Heliogen Blue K7096 from BASF), a monoazo pigment for yellow (e.g. Paliotol Yellow K1760 from BASF), etc.

[0049] Optionally, the material may also include diluents and/or plasticizers such as waxes (paraffins) or other processing resins (terpenics, phenolics, etc.) to facilitate processing during manufacture, all of these diluents and plasticizers being between 0 and 5% by weight.

By way of example and as represented in FIG. 3, the material comprises the metallic filler M and/or the ceramic filler 2 with polyamide as polymer 4 and polyurethane as coupling agent 3 with preferably at least 20 carbon atoms. carbon. In this example, the hydrogen bond between the polymer, the coupling agent and the load is symbolized by dotted lines. More specifically, for this composition, the material comprises, for a percentage by weight of 100%, the metallic filler such as a stainless steel and/or ceramic such as a zirconium oxide in a percentage of between 65 and 80%, preferably between 65 and 75%, the polyamide in a percentage of between 19.5 and 34.5%, preferably between 24 and 34%, and the polyurethane in a percentage of between 0.5 and 5%, preferably between 1 and 3.5%.

[0051] For example, the material comprises a metallic and/or ceramic filler and polyurethane with the polyurethane acting both as a polymer and as a coupling agent. In this example, no coupling agent separate from the polymer is therefore required because the interaction between the filler and the polymer is sufficient to ensure good cohesion of the material at the end of the process.

By way of example, the material comprises a metallic and/or ceramic filler with polyamide as polymer and as coupling agent a hydroxysilane with an amide or amine function, the coupling agent advantageously comprising at least 20 carbon atoms .

[0053] By way of example, the material comprises a metallic and/or ceramic filler with polyester as polymer and as coupling agent a hydroxysilane with an amide or amine function, the coupling agent preferably comprising at least 20 carbon atoms .

[0054] The article is manufactured by injection molding or by 3D printing. The process is characterized by the BET of the filler powder which must be sufficient to obtain a reactive surface. More specifically, the base material for the filler is a powder having a BET specific surface greater than or equal to 0.01 m ² /g, preferably 2 m ² /g, more preferably 5 m ² /g measured according to the ISO standard 9277 from 2010. For injection molding, the manufacturing process comprises the following steps referring to the fillers, polymers, coupling agents, reinforcement and pigments described above: a) Prepare granules of a few millimeters comprising by weight: the metallic filler and / or ceramic having a density greater than or equal to 3 g/cm ³ , the filler being present in a percentage greater than 50% and less than or equal to 85%, preferably between 60 and 80% and more preferably between 65 and 75% , the polymer(s) present as a whole in a percentage greater than or equal to 15% and less than or equal to 50%, preferably between 20 and 40% and more preferably between 25 and 35%, optionally at least one coupling agent present in a percentage greater than or equal to 0% and less than 10%, advantageously between 0.1 and 10%, more advantageously between 0.1 and 5%, even more advantageously between 0.5 and 3%, optionally a reinforcement present in a percent age comprised between 0 and 10%, optionally the pigment(s) present in a percentage comprised between 0 and 5%, optionally the diluent and/or the plasticizer or a mixture of diluents and/or plasticizers, said diluent and/or said plasticizer or said mixture of diluents and/or plasticizers being present in a percentage comprised between 0 and 5%. b) Injection molding said pellets to form the article. The injection is carried out in a mold which has a temperature of between 60 and 100°C, preferably between 70 and 80°C, while the material during the injection has a temperature of between 200 and 300°C, and , preferably between 250 and 300°C.

In step a), the granules can be manufactured by cutting a sausage from the extrusion of the aforementioned raw materials. Advantageously, the coupling agent, if present, is initially introduced into a hopper of the extruder either separately or with the polymer granules before introducing the metal or ceramic powder in a second step into the extruder. When the coupling agent is introduced separately, it can be introduced in powder form with a d90 less than or equal to 500 μm and, preferably, 315 μm or in liquid form. The pigment can be introduced during extrusion and advantageously subsequently. It is also possible to mix it with the polymer granules just before extrusion.

According to a variant, the metallic or ceramic material and the coupling agent, if present, are first introduced into a hopper of the extruder so as to coat the metallic or ceramic powder. , with the coupling agent before introducing the polymer and the reinforcement.

Alternatively, the article can be manufactured by 3D printing such as by FDM (Fusion Deposition Molding).

The article thus obtained comprises the metallic material, and/or ceramic, and the plastic material comprising the polymer, and optionally the coupling agent, with products resulting from the reaction between the filler, the polymer and the coupling agent during extrusion or injection. It also includes the reinforcement and the pigment, if there is pigment and reinforcement. It has a Young's modulus greater than or equal to 2.5 GPa, an elongation at break greater than or equal to 5% and a breaking load greater than or equal to 30 MPa, these properties being measured according to the ISO standard. 527-1 A of 2019. [0061] By way of example, tests have been carried out to manufacture casebands by injection, starting from cylindrical granules having a diameter and a length respectively of the order of 4 mm and 1.5 mm. Tables 1 and 2 below show two examples with the resulting properties before and after aging for 24 hours in a ventilated oven without humidity control at 60°C in table 3. Resilience tests by pendulum hammer on the casebands have moreover demonstrated the good tenacity of the casebands produced with the aforementioned compositions.

Table 1 - Example 1 - Composition

Table 2 - Example 2 - Composition

Table 3 - Examples 1 and 2 - Properties before and after aging between ()

Claims

1. Article made of a material having a density between 2 and 7 g/cm ³ , the material comprising by weight for a total of 100%:

- a filler (2) in a metallic and/or ceramic material having a density greater than or equal to 3 g/cm ³ , said filler

(2) being present in a percentage greater than 50% and less than or equal to 85%,

- at least one polymer (4) present in a percentage greater than or equal to 15% and less than or equal to 50%, - optionally at least one coupling agent (3) present in a percentage greater than or equal to 0% and less than

10%,

- optionally at least one reinforcement present in a percentage comprised between 0 and 10%, - optionally at least one pigment present in a percentage comprised between 0 and 5%,

- optionally at least one diluent and/or one plasticizer present in a percentage of between 0 and 5%, said polymer (4) being bound to the filler (2) and/or, when the material comprises at least one coupling agent ( 3), the coupling agent (3) being respectively linked to the polymer (4) and to the filler (2) by one or more of the bonds chosen from among a hydrogen bond, a coordination bond and an ionic bond.

2. Article according to claim 1, characterized in that the filler (2) is present in a percentage by weight of between 60 and 80% and in that the polymer (4) is present in a percentage of between 20 and 40% .

3. Article according to claim 1 or 2, characterized in that the filler (2) is present in a percentage by weight of between 65 and 75% and in that the polymer (4) is present in a percentage of between 25 and 35%.

4. Article according to one of the preceding claims, characterized in that the coupling agent (3) is present in a percentage by weight of between 0.1 and 10%.

5. Article according to the preceding claim, characterized in that the coupling agent (3) is present in a percentage by weight of between 0.1 and 5%.

6. Article according to claim 4 or 5, characterized in that the coupling agent (3) is present in a percentage by weight of between 0.5 and 3%.

7. Article according to one of the preceding claims, characterized in that the metallic and/or ceramic material comprises on the surface oxides, hydroxides and/or electronic vacancies involved in the hydrogen, coordination and ionic bonds with the polymer ( 4) and/or the coupling agent (3).

8. Article according to one of the preceding claims, characterized in that the polymer (4) and/or the coupling agent (3) carry one or more of the groups chosen from NH _X , OH, COC, C =0 and COOH.

9. Article according to one of the preceding claims, characterized in that a bond is a hydrogen bond, the polymer (4) and/or the coupling agent (3) comprising a group bearing a hydrogen atom which is a hydrogen bond donor and a group bearing an element more electronegative than hydrogen which is a hydrogen bond acceptor, said bond being established with a hydroxide and oxide group at the surface of the charge (2).

10. Article according to claim 9, characterized in that said element is chosen from oxygen, nitrogen, chlorine, bromine and fluorine.

11. Article according to claim 9 or 10, characterized in that the respectively hydrogen bond donor and acceptor groups are adjacent on the polymer (4) and/or on the coupling agent (3).

12. Article according to the preceding claim, characterized in that the polymer (4) and/or the coupling agent (3) comprises a hydrogen bond donor which is an NH _X group and a hydrogen bond acceptor which is a group C=0.

13. Article according to the preceding claim, characterized in that the polymer (4) is a polyamide.

14. Article according to claim 12 or 13, characterized in that the coupling agent (3) is a polyurethane.

15. Article according to one of the preceding claims, characterized in that a bond is an ionic bond with the polymer (4) bearing an NH _X + group linked to an anion of the filler (2) and/or of the coupling agent (3).

16. Article according to the preceding claim, characterized in that the filler (2) carries an O- anion.

17. Article according to claim 15 or 16, characterized in that the coupling agent (3) carries an R-COO- anion.

18. Article according to one of the preceding claims, characterized in that a bond is a coordination bond with the polymer (4) and / or the coupling agent (3) carrying amine or carboxylic acid functions forming said bond with an electron gap at the surface of the charge (2).

19. Article according to one of claims 4 to 18, characterized in that the coupling agent (3) comprises at least 20 carbon atoms.

20. Article according to one of the preceding claims, characterized in that said material comprises the filler (2) and the polymer (4) which is a polyurethane, without addition of said coupling agent (3).

21. Article according to one of claims 4 to 19, characterized in that said material comprises the filler (2) with polyamide as polymer (4) and polyurethane as coupling agent (3).

22. Article according to the preceding claim, characterized in that said material comprises, for a percentage of 100%, said filler (2) in a percentage of between 65 and 80%, said polymer (4) in a percentage of between 19.5 and 34.5%, and said coupling agent (3) in a percentage of between 0.5 and 5%.

23. Article according to the preceding claim, characterized in that said material comprises said filler (2) in a percentage of between 65 and 75%, said polymer (4) in a percentage of between 24 and 34%, and said coupling agent (3) in a percentage between 1 and 3.5%.

24. Article according to one of claims 4 to 19, characterized in that said material comprises the filler (2) with polyamide as polymer (4) and as coupling agent (3) a hydroxysilane with an amide or amine function.

25. Article according to one of claims 4 to 19, characterized in that said material comprises the filler (2) with polyester as polymer (4) and as coupling agent (3) a hydroxysilane with an amide or amine function.

26. Article according to one of the preceding claims, characterized in that the reinforcement is present in a percentage by weight of between 1 and 6%.

27. Article according to one of the preceding claims, characterized in that said reinforcement is formed of glass fibers, glass beads, carbon fibers and / or aramid fibers.

28. Article according to one of the preceding claims, characterized in that it is a dressing component or watch movement.

29. Method for manufacturing an article according to one of the preceding claims, comprising: a) a step of providing the base materials for the filler (2), the polymer (4), and optionally the coupling (3), the reinforcement and the pigment, with:

- the filler (2) in a metallic and/or ceramic material having a density greater than or equal to 3 g/cm ³ , said filler (2) being present in a percentage greater than 50% and less than or equal to 85%,

- the polymer (4) present in a percentage greater than or equal to 15% and less than or equal to 50%,

- the coupling agent (3) present in a percentage greater than or equal to 0% and less than 10%, - the reinforcement present in a percentage between 0 and

10%,

- the pigment present in a percentage between 0 and 5%,

- the diluent and/or the plasticizer present in a percentage of between 0 and 5%, b) a step of shaping the base materials to produce the article by an injection molding technique or by a 3D printing technique, the method being characterized in that the base material for the filler (2) is a powder having a BET specific surface greater than or equal to 0.01 m ² /g, preferably 2 m ² /g, more preferably 5 m ² /g and in that, after the shaping step, said polymer (4) is bonded to the filler (2) and/or, when the material comprises at least one coupling agent (3), the coupling agent (3) is respectively linked to the polymer (4) and to the filler (2) by one or more of the bonds chosen from among a hydrogen bond, a coordination bond and an ionic bond.