Item made of heavy plastic material

Abstract

To provide an item made of a heavy plastic material for enhancing the cohesion of the material and thereby the mechanical properties of the material.SOLUTION: An item is made of a material including by weight: a metallic and / or ceramic filler present in a percentage 50% or more and 85% or less, at least one polymer present in a percentage 15% or more and 50% or less, and optionally at least one coupling agent present in a percentage 0% or more and less than 10%. The polymer is bonded to the filler and / or, when the material includes at least one coupling agent, the coupling agent is respectively bonded to the polymer and to the filler by one or more hydrogen bonds. The polymer, and / or the coupling agent, includes a hydrogen bond donor which is a group NHX adjacent to a hydrogen bond acceptor which is a group C=O; so as to form a unit -[(C=O)NH]-, and the unit -[(C=O)NH]- represents at least 1% molar of the polymer, and / or the coupling agent.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to articles made from heavy impact-resistant plastic materials, such as components of timepieces.

[0002] The present invention also relates to a method for manufacturing such articles made from heavy plastics.

Background Art

[0003] Many external component parts, such as intermediate parts and bands, are made from plastic materials. These components can be produced using a molding method, which offers the advantage of being able to obtain various shapes without any modification work. These plastic material components have a density close to 1 and thus are characterized by being lightweight. This is a drawback for users who require the wearing of a wristwatch with a specific weight on the wrist.

[0004] To improve this drawback, for example, in European Patent No. 2482142, it is proposed to produce timepiece components of plastic materials filled with high-density metal powders such as tungsten powder, whether they are movements or external component parts. These components are produced using an injection molding method, which enables the retention of the advantages of molding in the mold without subsequent modification, while increasing the density of the components.

[0005] Therefore, these materials combine the advantages of plastics such as ease of injection molding with the advantages of metals such as density, cold touch, and metallic appearance.

[0006] However, compared to the host polymer matrix, a decrease in resistance to breakage and elongation may be observed in these materials. This decrease is due to the poor bonding of the material, caused by incorporating micrometer-sized metal powders into nanometer-sized polymer chains. Therefore, this reduction in properties due to poor bonding of the material is observed in materials containing metals (or ceramics) as fillers, polyolefins (polyethylene, polypropylene) as polymers, and polyurethanes as binders.

[0007] This reduction in mechanical properties affects the impact absorption capacity of the material. Therefore, this type of material is not suitable for applications that require impact resistance, such as in the field of chronographs that produce intermediate parts, etc.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] An object of the present invention is to provide a novel and heavy plastic material composition that improves the bonding strength of the material and thereby improves the mechanical properties of the material.

[0010] The present invention has found particularly interesting applications in the field of watchmaking. However, the invention is not limited to such applications.

Means for Solving the Problems

[0011] For this purpose, the present invention provides an article, the article being, in total weight of 100%, - 3 g / cm 3 a filler made of a metal and / or ceramic material having a density of or more, and wherein the filler is present in a percentage of 50% or more and 85% or less, the filler, at least one polymer present in a percentage of - 15% or more and 50% or less, and , optionally, at least one binder present in a percentage of 0% or more and less than 10%, the binder, optionally, at least one reinforcing agent 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 extender and / or plasticizer present in a percentage between 0 and 5% and is made of a material containing the same.

[0012] According to the present invention, the polymer is bonded to the filler and / or, when the material contains at least one binder, the binder is bonded to each of the filler and the polymer by one or more hydrogen bonds.

[0013] The polymer and / or the binder contains a hydrogen bond donor, and the hydrogen bond donor is an NH group adjacent to a hydrogen bond acceptor which is a C = O group so as to form a -[(C = O)NH]- unit. X

[0014] The -[(C = O)NH]- unit corresponds to at least 1 mol% of the polymer and / or the binder.

[0015] These hydrogen bonds that bond the filler, the polymer, and, when applicable, the binder, to the material​​​​ enable the guarantee of good bonding strength. These hydrogen bonds typically have an interaction energy of 100 kJ / mol or less than 50 kJ / mol, and during the manufacturing process, as the temperature rises it can break the intermolecular bonds, and after cooling and bond regeneration, it has the characteristics of ensuring better mixing and better bonding strength of the material.

[0016] The material according to the present invention has sufficient rigidity with a Young's modulus of 2.5 GPa or more, sufficient elongation at break of 5% or more, and sufficient tensile strength of 30 MPa or more for the use of a chronometer. The material according to the present invention further has good toughness and a density between 2 and 7 g / cm 3 .

[0017] In addition to these characteristics described in the previous paragraphs, the article according to the present invention may have one or more complementary characteristics considered based on the following individual criteria or by any technically possible combination: - The filler is present in a weight percentage between 60 and 80%, and the polymer is present in a weight percentage between 20 and 40%. - The filler is present in a weight percentage between 65 and 75%, and the polymer is present in a weight percentage between 25 and 35%. - The filler is present in a weight percentage between 50 and 75%, and the polymer is present in a weight percentage between 25 and 50%. - The filler is present in a weight percentage between 50 and 65%, and the polymer is present in a weight percentage between 35 and 50%. - The binder is present in a weight percentage between 0.1 and 10%. - The binder is present in a weight percentage between 0.1 and 5%. - The binder is present at a weight percentage between 0.5 and 3%, - The metal and / or ceramic material is included within surface oxides, hydroxides, and / or electrons within hydrogen, comprising coordination and ionic bonds with the polymer and / or binder on the holes, - The polymer and / or binder has one or more groups selected from X NH, OH, COC, C=O, and COOH, - The polymer is a polyamide, preferably polyamide 11, - The binder is a polyurethane, - The polymer is bonded to the filler and / or when the material includes at least one binder, the binder is bonded to each of the polymer and the filler by one or more ionic bonds, and the polymer has an NH + group bonded to the anions of the filler and / or binder, - The filler has an O-anion, X - The binder has an R-COO-anion, - The polymer is bonded to the filler and / or when the material includes at least one binder, the binder is bonded to each of the polymer and the filler by one or more coordination bonds, and the polymer and / or binder has an amine or carboxylic acid functional group that generates the coordination bond with the electron holes on the surface of the filler, - The binder contains at least 20 carbon atoms, - The material includes the filler and a polymer that is a polyurethane, without adding the binder, - The material includes the filler, a polyamide as the polymer, and a polyurethane as the binder, - The material is at 100% percentage and at a percentage between 65 and 80% of the said amine or carboxylic acid functional group that generates the coordination bond with the electron holes on the surface of the filler, - The binder contains at least 20 carbon atoms, - The material includes the filler and a polymer that is a polyurethane, without adding the binder, - - The material includes the filler, a polyamide as the polymer, and a polyurethane as the binder, - - The material is at 100% percentage and at a percentage between 65 and 80% of the said A filler, the polymer in a percentage between 19.5 and 34.5%, and the binder in a percentage between 0.5 and 5% are included, - The material is, in 100% percentage, the filler in a percentage between 65 and 75% of the said filler, the polymer in a percentage between 24 and 34% of the said polymer, and the binder in a percentage between 1 and 3.5% of the - The material is, in 100% percentage, the filler in a percentage between 50 and 75% of the said filler, the polymer in a percentage between 24.5 and 49.5% of the said polymer, and the binder in a percentage between 0.5 and 5% are included, - The material is, in 100% percentage, the filler in a percentage between 50 and 65% of the said filler, the polymer in a percentage between 34.5 and 49.5% of the said polymer, and the binder in a percentage between 0.5 and 5% are included, - The material includes a filler having polyamide as the polymer and an amide or hydroxysilane having an amine functional group as the binder, - The reinforcing agent is present in a weight percentage between 1 and 6%, - The reinforcing agent is formed from glass fibers, glass beads, carbon fibers and / or aramid fibers and the like, - The article is an external part of a timepiece or a movement component.

[0018] Furthermore, the present invention relates to a method for manufacturing this material by molding, injection or 3D printing.

[0019] The method, when the polymer and / or the binder are present, includes hydrogen bonding with the binder and any To obtain a filler having a reaction surface area sufficient to generate complementary ionic and / or coordination bonds such that the base material of the filler is 0.01 m 2 / g, preferably 2 m 2 / g, more preferably 5 m 2 / g or more and is in the form of a powder having a BET. Therefore , the reaction surface area includes hydroxides, oxides and / or electron holes regardless of the type of ceramic (oxide, nitride or carbide) or metal (steel, tungsten sten, etc.).

[0020] Further features and advantages of the present invention will become apparent from the following description of preferred embodiments shown as non-limiting examples with reference to the accompanying drawings.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0022] The present invention relates to an article made from a composite material including a plastic material and a metal or ceramic material.

[0023] For example, the article can be a component such as a wristwatch, jewelry, a band, etc.

[0024] The article can also be a component of the bezel, for example, a base, an arm, a substrate.

[0025] ​​In a non-limiting and non-exhaustive manner, an article according to the present invention can be an article for sports equipment, a cooking utensil article, a music article or musical instrument, a leather article or sewing supplies article, a component of an automobile or aircraft (e.g., a phone protective case, a computer keyboard , keys of a computer keyboard, a headset, etc.), a component such as a writing instrument, or can form these as a whole.

[0026] Advantageously, the article is a component or part of a component, and these functions require specific resistance to collisions and impacts.

[0027] In the specific field of watchmaking, this article can be, for example, external component elements such as intermediate parts, back covers, bezels, buttons, band loops, dials, hands, scale marks on the dial, etc.

[0028] As an example, an intermediate part 1 made from the material of the present invention is shown in FIG. 1.

[0029] According to an example of another embodiment (not shown), an article according to the present invention can be, for example, a component of a movement such as a plate.

[0030] According to the present invention, the article is made from a material comprising two main components which are a metal and / or ceramic filler and a polymer. Thus, the material can be said to be a composite material.

[0031] Optionally, the material can contain one or more binders if the physico-chemical interaction between the filler and the polymer is not sufficient according to the type of application, and if it is required to further increase the impact resistance of the material of the present invention which has already been strengthened.

[0032] Optionally, the material can also contain a reinforcing agent.

[0033] Optionally, the material may also include one or more pigments.

[0034] Optionally, the material may also include a spreading agent and / or a plasticizer.

[0035] The filler can be a metal and / or a ceramic.

[0036] The metal material can be composed of conventional carbon steel, stainless steel, copper, copper alloy, titanium, titanium alloy or tantalum. Preferably, the metal material is composed of nickel-free stainless steel. It is composed.

[0037] The ceramic material can be composed of carbides, nitrides or oxides such as ZrO2, CeO2, ZnO, etc. It can be composed.

[0038] The filler can also be composed of a filler containing a mixture of a metal material and a ceramic material.

[0039] The filler is present in a weight percentage of 50% or more and 85% or less of the weight of the material.

[0040] For example, the filler is between 50 and 75% of the (total) weight of the material.

[0041] For example, when a material with a relatively low density is required, the filler is between 50 and 65% of the (total) weight of the material. It is between 50 and 65%.

[0042] For example, when a further increase in the material density is required, the filler is between 60 and 80% of the (total) weight of the material, for example, between 65 and 75% by weight. It is between 60 and 80%, for example, between 65 and 75% by weight.

[0043] Advantageously, in the above examples, the filler is, as a whole, the majority by weight, i.e., it exceeds 50% of the weight of the material. It exceeds 50% of the weight of the material.

[0044] According to the present invention, the filler is introduced in the form of a powder having a high specific surface area (≧0.01 m 2 / g) during the manufacturing process, and this powder, in fact, has on its surface a composition modifier and / or defects regardless of the type of metal or ceramic packing material in the absence of a specific treatment. The filler can be composed of oxides or hydroxides present on the oxidized surface of the powder and defects such as electron holes, thereby enabling various hydrogen bonding interactions with the binder when the polymer and / or binder is present. Therefore, FIG. 2 schematically shows the interaction established between the surface of the filler 2 and the binder 3 and the polymer 4 when the material contains a binder.

[0045] The material contains one or more polymers capable of forming hydrogen bonds in addition to ionic and / or coordination bonds with the filler and / or the binder when the binder is present. All such physicochemical bonds and especially hydrogen bonds are characterized by having a low interaction energy typically between 5 and 100 kJ / mol, enabling the breaking of intermolecular bonds during the temperature rise during the injection or 3D printing of the material. These physicochemical bonds are regenerated during the cooling of the material after injection or 3D printing. This feature enables better mixing between the components, better compatibility, and thus better bonding force of the material at the molecular scale and, therefore, better overall bonding force of the material.

[0046] The polymer or set of polymers corresponds to a weight percentage between 15 and 50% of the (comprehensive) material.

[0047] For example, the polymer or set of polymers is between 25 and 50% by weight of the (comprehensive) material.​​​​​​​ corresponds to a weight percentage.

[0048] For example, the polymer or set of polymers corresponds to a weight percentage between 35 and 50% of the (comprising) material. corresponds to a weight percentage.

[0049] For example, the polymer or set of polymers corresponds to a weight percentage between 20 and 40%, for example, between 25 and 35% of the (comprising) material. corresponds to a weight percentage.

[0050] If the filler is the majority of the material, the polymer or set of polymers will be less than 50% by weight. percentage.

[0051] Advantageously, the polymer or set of polymers is selected to form hydrogen bonds with the filler. For this purpose, the polymer or set of polymers contains a hydrogen bond donor containing a group having a hydrogen atom such as an NH or OH group, and a hydrogen bond acceptor containing a group having an atom more electronegative than hydrogen, such as an atom of a nitrogen, oxygen, or halogen group such as fluorine, chlorine, bromine. The hydrogen bonds are formed by the hydroxides and oxides present on the oxidized surface of the metal or ceramic filler. For example, the hydroxide groups on the surface of the filler interact with the C=O, R-OH, COC, R-NH-R' groups of the polymer. R’ groups of the polymer. The hydrogen bonds are formed by the hydroxides and oxides present on the oxidized surface of the metal or ceramic filler. are formed.

[0052] For example, the hydroxide groups on the surface of the filler interact with the C=O, R-OH, COC, R-NH R’ groups of the polymer. X R’ groups of the polymer.

[0053] Preferably, the hydrogen bond donor and acceptor are adjacent on the polymer chain.

[0054] Preferably, the polymer or set of polymers contains a hydrogen bond donor, and the hydrogen bond donor is a C=O group so as to form a -[(C=O)NH]- unit with a hydrogen bond acceptor which is a C=O group. ceptor which is a C=O group so as to form a -[(C=O)NH]- unit. NH adjacent to the septum X is a group.

[0055] Preferably, the polymer or set of polymers can be a poly amide of the R-C(=O)-NH-R’ chain, thus containing -[(C=O)NH]- units, and thus the C=O group containing a binding acceptor oxygen atom and the N-H group containing a binding donor hydrogen atom are adjacent to each other.

[0056] Preferably, the -[(C=O)NH]- unit corresponds to at least 1% of the polymer or set of polymer chains.

[0057] Preferably, the polymer is a polyamide from a renewable source of biological origin, such as polyamide 11.

[0058] Furthermore, ionic and / or coordination bonds are formed between the polymer and the filler, generating further mutual actions and further strengthening the binding force of the material.

[0059] The ionic bond in the scope of the present invention results from the interaction between a negatively charged basic functional group and a positively charged acidic functional group. The ionic bond is generated by transferring H ions from the OH groups on the surface of a metal or ceramic filler to the polymer + For example, the polymer can be a polyamide containing an NH group, and more specifically, after an acid-base reaction, R-NH X X +1 -R’+ / MO- can be obtained.

[0060] A coordination bond is a special covalent bond, and the doublet of shared electrons is obtained from only one of the atoms, contrary to the conventional covalent bond where one electron is obtained from each of the bonding electrons. In the present invention ​ According to this, this coordination bond requires, more specifically, a Lewis base produced by the polymer and is associated with an electron hole on the surface of the filler that generates a Lewis acid. Any polymer having a functional group containing an atom having an unshared pair can share this pair so as to "stabilize" the electron hole. For example, the polymer can be composed of an unshared pair of nitrogen or oxygen in R(C=O)NR', RO(C=O)NR' and R(C=O)OR'. The polymer can also have an amine (NH X ) or carboxylic acid (COOH) functional group, and the amine (NH X ) or carboxylic acid (COOH) functional group can form this coordination bond with the electron hole on the surface of the filler. For example, polyurethane and polyester can be mentioned.

[0061] The material can contain a binder in a percentage between 0% and less than 10%, preferably between 0.1 and 10%, more preferably between 0. 1 and 5%, even more preferably between 0.5 and 3%.

[0062] The use of the binder makes it possible to further enhance the mechanical properties, especially the impact resistance, of articles made from such materials according to the present invention.

[0063] The binder can be mainly bonded to the filler and the polymer by one or more hydrogen bonds. The hydrogen bonds between the filler and the binder and between the polymer and the binder can replace the hydrogen bonds between the polymer and the filler or supplement the hydrogen bonds between the polymer and the filler according to the nature of the polymer used.

[0064] The ionic and / or coordination bonds described above also generate further interactions and the binding force of the material​​​​​​​​ That is, the binding force between the binder and the filler and between the binder and the polymer can be further strengthened.

[0065] In the presence of the binder, hydrogen bonds are mainly formed between the binder and the filler and between the binder and the polymer, and it is specified that there is not necessarily a direct hydrogen bond between the filler and the polymer. Regarding the polymer, the binder may contain at least one group selected from C=O, COC, OH, NH or COOH. X or COOH.

[0066] Preferably, the hydrogen bond donor and acceptor are adjacent on the chain of the binder.

[0067] Preferably, the binder contains a hydrogen bond donor, and the hydrogen bond donor is an NH group adjacent to a hydrogen bond acceptor which is a C=O group so as to form a -[(C=O)NH]- unit. X group.

[0068] Preferably, the -[(C=O)NH]- unit corresponds to at least 1% of the chain of the binder. to.

[0069] Preferably, the binder is a polyurethane containing a -[O-C=O-NH]- unit. .

[0070] Preferably, the binder has a long chain of at least 20 carbon atoms.

[0071] Also by way of example, the binder is a hydroxysilane having an amide or amine functional group on the chain and advantageously having at least 20 carbon atoms, which can enable hydrogen, ionic and / or coordination bonds. to be possible.

[0072] Also by way of example, the binder can also be ionic H from the OH groups on the surface of the filler.+ By moving, During the manufacturing process, an acid-base reaction occurs between the filler and the binder to generate an ionic bond can be formed.

[0073] The binder can also generate an ionic bond between the binder and the polymer. The polymer generates a base Contains one or the other of the carboxylic acid COOH and amine R'-NH X functional groups respectively, and after the acid-base reaction, RCOO- / R'-NH +1+ is obtained. X

[0074] Alternatively, the polymer and the binder may already be charged before contact. In this case, In the case of the above example, the binder and the polymer each have a basic functional group RCOO- or an acidic functional group R'-NH X+1 +.

[0075] Optionally, the material may also contain a reinforcing agent (inclusive) in a weight percentage between 0 and 10%, preferably between 0% (excluding 0%) and 10% or less, advantageously between 1 and 6%. The reinforcing agent can be present in various forms, for example, in the form of fibers or particles. For example, the reinforcing agent can be composed of glass fibers, glass beads, carbon fibers and / or aramid fibers, and has a fiber length of 300 μm or less, and preferably 200 μm. The purpose of the reinforcing agent is to strengthen the toughness of the material, limit the shrinkage of the material during injection, and / or enhance the conductivity of the material.

[0076] Optionally, the material may also contain one or more pigments in a total percentage by weight between 0 and 5%, preferably between 0% (excluding 0%) and 5% or less of. The pigment may be an organic pigment or an inorganic pigment. For example, the pigment is carbon black for black, red for Diketopyrrolopyrrole for red (e.g., Irgazin Red K3840L from BASF) W), copper phthalocyanine for blue (e.g., Heliogen Blue from BASF) K7096), monoazo pigment for yellow (e.g., Paliotol Yellow from BASF) llow K1760), etc. and can be composed of these.

[0077] Optionally, the material also includes spreading agents and / or plasticizers such as wax (paraffin) or resins for other uses (terpenes, phenols , etc.), which can facilitate the mounting during manufacturing. All of these spreading agents and plasticizers are between 0 and 5% by weight, preferably between 0% (excluding 0%) and 5% or less by weight.

[0078] For example, as represented by FIG. 3, the material includes a metal filler M and / or a ceramic filler 2, a polyamide as the polymer 4, and a polyurethane as the binder 3 preferably having at least 20 carbon atoms . Preferably, the polymer 4 is polyamide 1 11.

[0079] Since polyamide P11 is obtained from castor oil, it is a renewable source. Therefore , the material provided by the present invention is a bio-derived material.

[0080] In this example, the hydrogen bonds between the polymer, the binder, and the filler are represented by dotted lines.

[0081] For example, for 100% by weight percentage, - a metal filler such as stainless steel in a percentage between 65 and 80% by weight, for example, between 65 and 75% by weight, or between 50 and 75 % by weight, for example, between 50 and 65% by weight, and / or a ceramic filler such as zirconium oxide, and - Between 19.5 and 34.5% by weight, for example, between 24 and 34%, or between 24.5 and 49.5%, for example, between 34.5 and 49.5% of polyamide by percentage, and - Between 0.5 and 5% by percentage, for example, between 1 and 3.5% of polyurethane, and contains.

[0082] For example, the material is, based on 100% weight percentage, - Between 65 and 80% by weight, for example, between 65 and 75%, or between 50 and 75 % by weight, for example, between 50 and 65% of a ceramic filler such as zirconium oxide, and - Between 19.5 and 34.5% by weight, for example, between 24 and 34%, or between 24.5 and 49.5%, for example, between 34.5 and 49.5% of polyamide such as polyamide 11, etc., - Between 0.5 and 5% by percentage, for example, between 1 and 3.5% of polyurethane, and contains.

[0083] Such a material that combines a ceramic material and a bio-based material from a renewable source is called a bioceramic material.

[0084] For example, the material contains a metal and / or ceramic filler and polyurethane, and the polyurethane acts as both a polymer and a binder. Therefore, in this example, a separate binder from the polymer is not required. This is because the interaction between the filler and the polymer is sufficient to ensure good bonding strength of the material after this process.

[0085] For example, the material contains a metal and / or ceramic filler and polyamide as a polymer , including a hydroxy silane having an amide or amine functional group as a binder, and the binder is , preferably containing at least 20 carbon atoms.

[0086] For example, the material includes a metal and / or ceramic filler, a polyester as a polymer , and a hydroxy silane having an amide or amine functional group as a binder, and the binder preferably contains at least 20 carbon atoms.

[0087] The article is manufactured by molding, injection or 3D printing. The method is characterized in that the BET of the filler powder must be sufficient to obtain a reaction surface area. More specifically, the base material of the filler is a powder having a BET specific surface area of 0.01 m 2 / g or more, preferably 2 m 2 / g, more preferably 5 m 2 / g, measured according to the ISO9277 standard in 2010. .

[0088] In the case of injection molding, the manufacturing method includes the following steps referring to the filler, polymer, binder, reinforcing agent and pigment described above: a) A step of preparing granules of several millimeters, and the granules are, by weight, - A metal and / or ceramic filler having a density of 3 g / cm 3 or more, and the filler is present in a percentage of 50% or more and 85% or less, for example, between 60 and 80%, for example, between 65 and 75%, for example between 50 and 75%, for example, between 50 and 65%. - The filler - Overall, 15% or more and 50% or less, for example, between 20 and 40%, for example, 2 between 5 and 35%, for example, between 25 and 50%, for example, between 35 and 50%. The polymer(s) present in the pellet, - Optionally, in a percentage of 0% or more and less than 10%, preferably between 0.1 and 10%, more preferably between 0.1 and 5%, even more preferably between 0.5 and 3%, at least one binder, - Optionally, a reinforcing agent present in a percentage between 0 and 10%, - Optionally, a pigment(s) present in a percentage between 0 and 5%, - Optionally, a spreading agent and / or a plasticizer, or a mixture of a spreading agent and / or a plasticizer, wherein the spreading agent and / or the plasticizer, or the mixture of the spreading agent and / or the plasticizer is present in a percentage between 0 and 5%, of the spreading agent and / or the plasticizer, or a mixture of a spreading agent and / or a plasticizer comprising a step; b) Injecting the granules for forming an article or a part of an article, for example, by overmolding onto another part a step of injection molding the granules, and is included. The injection is carried out in a mold having a temperature between 60 and 100 °C, preferably between 70 and 80 °C, while the material during injection has a temperature between 200 and 300 °C, preferably between 250 and 300 °C.

[0089] In step a), the granules can be produced by removing the cylindrical body obtained from the extrusion molding of the above-mentioned raw materials. Advantageously, when a binder is present, the binder is introduced into the hopper of the extruder separately or together with the polymer granules in a first stage, and this introduction is carried out before introducing the metal or ceramic powder into the extruder in a second stage. When the binder is introduced separately, the binder has a d90 of 500 μm or less, preferably 315 μm. It can be introduced in the form of a powder or in the form of a liquid. The pigment can advantageously be introduced in a second stage during the extrusion process. It is also conceivable to mix the polymer with the granules immediately before extrusion .

[0090] According to an alternative embodiment, when a metal or ceramic material and a binder are present, the binder is introduced into the hopper of the extruder in the first stage so as to coat the metal or ceramic powder with the binder before introducing the polymer and the reinforcing agent.

[0091] Alternatively, the article can be manufactured by 3D printing such as FDM (Fused Deposition Modeling).

[0092] The article thus obtained comprises a metal and / or ceramic material, a plastic material containing a polymer, and optionally a binder, and the product results from the reaction between the filler and the polymer and the binder during extrusion or injection. The article further comprises a reinforcing agent and a pigment, if present.

[0093] The article according to the invention has a Young's modulus of 2.5 GPa or more, an elongation at break of 5% or more, and a tensile strength of 30 MPa or more, and these properties are measured according to the ISO 527-1A standard of 2019 .

[0094] For example, tests were conducted to manufacture intermediate parts by injection from cylindrical granules having a diameter of about 4 mm and a length of about 1.5 mm.

[0095] Hereinafter, Tables 1 and 2 take two example embodiments and are accompanied by the properties obtained before and after 24 hours of conditioning in a ventilated oven without humidity control at 60 °C. Eye ​The Zot mechanical elasticity test further exhibited good toughness of the intermediate parts produced by the composition described above. It did.

[0096] Table 3 shows an example of the material composition according to the present invention without using a binder.

[0097] Table 4 shows the composition Comp1 of an article made from a heavy plastic material according to the prior art, in particular according to document EP3674816. from.

[0098] Table 5 shows the first variant Comp2 of the prior art composition Comp1 without using reinforcing fibers. p2 is shown.

[0099] Table 6 shows the second variant Comp3 of the prior art composition Comp1, and the ratios of the filler, polymer and binder are the same as those in the examples according to the present invention Inv1 and Inv2. Such a variant allows highlighting the advantages and improvements with respect to the binding force of the materials obtained with respect to the materials described in document EP3674816. and. For such a variant, it is possible to highlight the advantages and improvements with respect to the binding force of the materials obtained with respect to the materials described in document EP3674816. to.

[0100] Table 7 is a summary table gathering the various rigidity, elongation at break and breaking stress characteristics of the compositions according to the present invention (Inv1, Inv2, Inv3) and the prior art compositions (Comp1 , Comp2, Comp3). is.

[0101] By comparing Example 1 (Inv1), Example 2 (Inv2) and Example 3 (inv3) with Example 4 (Co mp1), Example 5 (Comp2), Example 6 (Comp3) of the prior art, in particular by the formation of hydrogen bonds with the filler, the benefits of a specific selection of polymers that strengthen the binding force with the filler are shown. to. is shown.

[0102] The use of a good binder further enables the enhancement of article properties (Examples 3 and 1).

[0103] TIFF2025100687000002.tif91170 Table 1 - Example 1 - Inv1

[0104] TIFF2025100687000003.tif81170 Table 2 - Example 2 - Inv2

[0105] TIFF2025100687000004.tif71170 Table 3 - Example 3 - Inv3

[0106] TIFF2025100687000005.tif91170 Table 4 - Example 4 - Composition 1 (Comp1)

[0107] TIFF2025100687000006.tif71170 Table 5 - Example 5 - Composition 2 (Comp2) (Composition 1 without reinforcing fibers)

[0108] TIFF2025100687000007.tif71170 Table 6 - Example 6 - Composition 3 (Comp3)

[0109] TIFF2025100687000008.tif101170 Comparison of Examples 1, 2, 3, 4, 5 and 6 - ( ) are before and after leveling of properties

Explanation of symbols

[0110] 2 Filler 3 Binder 4 Polymer

Claims

1. An article made of a material having a density between 2 and 7 g / cm ３ wherein the material is 、in a total weight of 100%, -3 g / cm ３ Filling made of a metal and / or ceramic material having the above density a filler (2), wherein the filler (2) is present in a percentage of 50% or more and 85% or less, and a filler (2), - at least one polymer ( 4) present in a percentage of -15% or more and 50% or less, - optionally, at least one binder ( 3) present in a percentage of 0% or more and less than 10%, - optionally, at least one reinforcing agent 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 extender and / or plasticizer present in a percentage between 0 and 5%, comprising, wherein the polymer (4) is bonded to the filler (2) and / or when the material comprises at least one binder (3), the binder (3) is bonded to each of the polymer (4) and the filler (2) by one or more hydrogen bonds, characterized in that the polymer (4) and / or the binder (3) comprises a hydrogen bond donor, and the hydrogen bond donor is such that -[(C=O)NH]- units are formed, C= wherein the -[(C=O)NH]- units correspond to at least 1 mol% of the polymer (4) and / or the binder ( NH adjacent to a hydrogen bond acceptor which is an O group Ｘ and is a group 3), an article.

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

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

4. The filler (2) is present in a weight percentage between 50 and 75%, and the polymer (4) is present in a weight percentage between 25 and 50%, characterized in that the article according to claim 1.

5. The filler (2) is present in a weight percentage between 50 and 65%, and the polymer (4) is present in a weight percentage between 35 and 50%, characterized in that the article according to claim 1.

6. The binder (3) is present in a weight percentage between 0.1 and 10%, characterized in that the article according to claim 1.

7. ​ The binder (3) is present in a weight percentage between 0.1 and 5%. The article according to claim 6, characterized in that.

8. The binder (3) is present in a weight percentage between 0.5 and 3%. The article according to claim 6, characterized in that.

9. The metal and / or ceramic material contains coordination and ionic bonds with the polymer (4) and / or the binder (3) on electron holes contained in surface oxides, hydroxides, and / or hydrogen. The article according to claim 1, characterized in that.

10. The polymer (4) and / or the binder (3) has NH Ｘ , OH, COC, C=O and The article according to claim 1, characterized by having one or more groups selected from, etc. and COOH. The article according to claim 1.

11. The polymer (4) is a polyamide, preferably polyamide 11, characterized by. The article according to claim 1.

12. The binder (3) is a polyurethane, characterized by the article according to claim 11 。

13. The polymer (4) is bonded to the filler (2), and / or when the material contains at least one binder (3), the binder (3) is bonded to each of the polymer (4) and the filler (2) by one or more ionic bonds, and the polymer ( The article according to claim 1, characterized by having a group. The article according to claim 1, characterized by having a group. 4) NH that binds to the anions of the filler (2) and / or the binder (3) Ｘ + The article according to claim 1, characterized by having a group.

14. The filler (2) has O-anions, characterized by the article according to claim 13 The article according to claim 13.

15. The binder (3) has an R-COO-anion, characterized by the article according to claim 13 The article according to claim 13.

16. The polymer (4) is bonded to the filler (2), and / or when the material contains at least one binder (3), the binder (3) is bonded to each of the polymer (4) and the filler (2) by one or more coordination bonds, and the polymer (4 The article according to claim 1, characterized in that. The article according to claim 1, characterized in that. The article according to claim 1, characterized in that. The article according to claim 1, characterized by having an amine or carboxylic acid functional group that generates the coordination bond with electron holes on the surface of the filler (2). The article according to claim 1.

17. The binder (3) contains at least 20 carbon atoms, characterized by the article according to claim 6 The article according to claim 6.

18. The material includes the filler (2) and the polymer (4) which is a polyurethane, The article according to claim 1, characterized by not adding the binder (3).

19. The material includes the filler (2), a polyamide as the polymer (4), and a polyurethane as the binder (3), and is characterized by the article according to claim 6. The article according to claim 6, wherein the material includes the filler (2), a polyamide as the polymer (4), and a polyurethane as the binder (3).

20. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 80%, the polymer (4) in a percentage between 19.5 and 34.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 19. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 80%, the polymer (4) in a percentage between 19.5 and 34.5%. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 80%, the polymer (4) in a percentage between 19.5 and 34.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 19. The article according to claim 19, wherein the material includes the filler (2) in a percentage between 65 and 80%, the polymer (4) in a percentage between 19.5 and 34.5%, and the binder (3) in a percentage between 0.5 and 5%.

21. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 75%, the polymer (4) in a percentage between 24 and 34%, and the binder (3) in a percentage between 1 and 3.5%, and is characterized by the article according to claim 20. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 75%, the polymer (4) in a percentage between 24 and 34%. The material is 100% by percentage and includes the filler (2) in a percentage between 65 and 75%, the polymer (4) in a percentage between 24 and 34%, and the binder (3) in a percentage between 1 and 3.5%, and is characterized by the article according to claim 20. The article according to claim 20, wherein the material includes the filler (2) in a percentage between 65 and 75%, the polymer (4) in a percentage between 24 and 34%, and the binder (3) in a percentage between 1 and 3.5%.

22. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 75%, the polymer (4) in a percentage between 24.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 19. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 75%, the polymer (4) in a percentage between 24.5 and 49.5%. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 75%, the polymer (4) in a percentage between 24.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 19. The article according to claim 19, wherein the material includes the filler (2) in a percentage between 50 and 75%, the polymer (4) in a percentage between 24.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%.

23. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 65%, the polymer (4) in a percentage between 34.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 22. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 65%. The material is 100% by percentage and includes the filler (2) in a percentage between 50 and 65%, the polymer (4) in a percentage between 34.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%, and is characterized by the article according to claim 22. The article according to claim 22, wherein the material includes the filler (2) in a percentage between 50 and 65%, the polymer (4) in a percentage between 34.5 and 49.5%, and the binder (3) in a percentage between 0.5 and 5%.

24. The material includes the filler (2), a polyamide as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3), and is characterized by the article according to claim 6. The material includes the filler (2), a polyamide as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3). The article according to claim 6, wherein the material includes the filler (2), a polyamide as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3).

25. The material includes the filler (2), a polyester as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3), and is characterized by the article according to claim 6. The material includes the filler (2), a polyester as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3). The article according to claim 6, wherein the material includes the filler (2), a polyester as the polymer (4), and a hydroxy silane having an amide or amine functional group as the binder (3).

26. The reinforcing agent is present in a weight percentage between 1 and 6%, and is characterized by the article according to claim 1. The article according to claim 1, wherein the reinforcing agent is present in a weight percentage between 1 and 6%.

27. The reinforcing agent is formed from glass fiber, glass beads, carbon fiber, and / or aramid fiber, and is characterized by the article according to claim 1. The article according to claim 1, wherein the reinforcing agent is formed from glass fiber, glass beads, carbon fiber, and / or aramid fiber.

28. The article is characterized by being composed of external parts of a timepiece or movement components. The article according to claim 1.

29. A method for manufacturing the article according to claim 1, the method comprising: a) providing a substrate for the filler (2), the polymer (4) and optionally the binder (3), the reinforcing agent and the pigment, wherein the substrate is made from a material, the filler (2) is present in a percentage of 50% or more and 85% or less, - The filling material (2) is a metal and / or ceramic material having a density of 3 g / cm ３ or more - the polymer (4) is present in a percentage of 15% or more and 50% or less, - the binder (3) is present in a percentage of 0% or more and less than 10%, - the reinforcing agent is present in a percentage between 0 and 10%, - the pigment is present in a percentage between 0 and 5%, - the extender and / or the plasticizer is present in a percentage between 0 and 5%, a step; b) shaping the substrate to produce the article by an injection molding technique or a 3D printing technique a step, wherein after step b), the polymer (4) is bonded to the filler (2) and / or, if the material contains at least one binder (3), the binder (3) is bonded to each of the polymer (4) and the filler (2) by one or more hydrogen bonds, characterized in that the polymer (4) and / or the binder (3) contains a hydrogen bond donor, the hydrogen bond donor being a C=O group so as to form a (C=O)NH unit, including, for the filler (2), the base material is 0.01 m ２ / g, preferably 2 m ２ / g, more preferably 5 m ２ / g or more of the powder having a BET specific surface area, and the molding step the (C=O)NH unit corresponding to at least 1 mol% of the polymer (4) and / or the binder (3). ​ ​ ​ ​ NH adjacent to a hydrogen bond acceptor Ｘ group, and ​ ​

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