Articles made from mineral composite materials and methods for manufacturing the same

Abstract

To provide an article made of a mineral composite material, and a method for manufacturing the same.SOLUTION: A composite material comprises by weight: one or more thermoplastic resins that are at least partially bio-based, the total percentage of the one or more thermoplastic resins being between 20% and 74.9%; a mineral filler having a seashell-based mineral material and a porous silica-based mineral material derived from diatom skeletons, a percentage of the mineral filler being between 25% and 79.9%; and a dispersant, a percentage of the dispersant being between 0.1% and 5%; optionally a stain system, a percentage of the stain system being between 0% and 5%; optionally a reinforcing material, a percentage of the reinforcing material being between 0% and 8%; and / or optionally a coupling agent, a percentage of the coupling agent being between 0% and 5%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite material comprising at least one bio-based resin and a mineral filler. [Background technology]

[0002] So-called bioceramic materials are known in the prior art. These include mixtures of partially bio-based resins such as polyamide 11, which is more than 50% bio-based, and ceramics such as yttria-stabilized zirconia (YSZ). The known advantages of such composite materials are: -Colorability using conventional dyeing systems, -Zirconia's inherent density: 4.5 g / cm³ 3 Increased density of molded parts due to - Zirconia's inherent thermal conductivity: 2.5 W·m -1 ·K -1 Increase in the thermal conductivity of molded parts That is the case.

[0003] The drawbacks of this bioceramic material are that it uses a large amount of fossil resources in the resin and ceramic, and that when worn, it may produce an unpleasant odor due to bacteria that form on the material surface and feed on organic residues. This is because the materials present in the described composite material do not possess significant antimicrobial activity. [Overview of the Initiative]

[0004] This invention involves developing a novel mineral composite material to overcome the shortcomings of conventional bioceramic materials. This novel material must have as little ecological impact as possible, be optimized for comfort when in contact with the skin, be able to dissipate heat at the skin-wrist interface, and be anti-odor.

[0005] The composite material comprises one or more thermoplastic resins that are at least partially bio-based. The term "partially" is understood to mean that the one or more resins as a whole are 60% or more, preferably 85% or more, and more preferably 98% or more bio-based. Instead of ceramics used in the prior art, the composite material further comprises mineral materials derived from seashells, namely calcium carbonate (CaCO3) based, and porous silica derived from diatom skeletons.

[0006] CaCO3 is 2.5 W·m -1 ·K -1 It has a thermal conductivity equivalent to that of YSZ. The density of CaCO3 is 2.7 g·cm³. -3 It is 4.5 g·cm of zirconia. -3 Compared to other materials, it makes the composite material lighter to wear. Diatomaceous earth silica has antibacterial properties that prevent the generation of unpleasant odors. Also, when mixed with seashells, it improves the flow of powder in dispensers during the manufacturing process.

[0007] More specifically, the present invention relates to an article made of a composite material comprising the following by weight: - One or more thermoplastic resins that are at least partially biobased, and the total percentage of the one or more thermoplastic resins is 20% to 74.9%, - A mineral filler comprising a shell-based mineral material and a porous silica-based mineral material derived from diatom skeletons, wherein the percentage of the mineral filler is 25% to 79.9%. - A dispersant, wherein the percentage is 0.1% to 5%, preferably 0.1% to 1%. -Optionally, a staining system, where the percentage is between 0% and 5%. -Optionally, a reinforcement material whose percentage is between 0% and 8%. -Optionally, a coupling agent, wherein the percentage of the coupling agent is between 0% and 5%.

[0008] The present invention further relates to a method for manufacturing an article, comprising the following steps. a. A process for providing shell-based mineral materials and porous silica-based mineral materials derived from diatom skeletons. b. A step of providing one or more thermoplastic resins that are at least partially bio-based, c. A process of collecting, sorting, washing, crushing, and sieving seashells to retain only seashell particles with a particle size of 100 μm or less. d. A step of mixing seashell particles and porous silica, wherein the mixture forms a mineral filler. e. A step of mixing a mineral filler and one or more thermoplastic resins with a dispersant. f. Optionally, add a dyeing system, reinforcing agent and / or coupling agent to the mixture obtained in step e. g. A step of molding the mixture obtained in step e or step f to obtain an article. [Modes for carrying out the invention]

[0009] The present invention relates to an article made of a composite material comprising at least one primarily bio-based thermoplastic resin and calcium carbonate and porous silica-based mineral materials. The article may be, for example, a timepiece component. More specifically, it may be an external component selected from a non-exclusive list including a central section, a back section, a bezel, a crown, push pieces, bracelet links, a bracelet, a tongue buckle, a clasp, a dial, hands, and dial indices.

[0010] A composite material includes (or consists of) the following, based on the total weight of the composite material: -1 or more thermoplastic resins, wherein the total weight percentage is 20% to 74.9%, preferably 50% to 59.9%, and is one or more thermoplastic resins. If the resin mixture or single resin is used, the resin is 60% or more, preferably 85% or more, more preferably 98% or more bio-based, and the percentage of bio-based in the mixture or resin is measured according to standard ASTM D6866-22. The one or more thermoplastic resins are selected from polyamide 11 (PA11), polyamide 10 (PA10), polyamide 610 (PA610), polyethylene furanoate (PEF), polyurethane (PU), polyether block amide (PEBA), thermoplastic copolyester elastomer (TPC), thermoplastic polyurethane elastomer (TPU), thermoplastic polyolefin elastomer (TPO), thermoplastic vulcanized elastomer (TPV), and thermoplastic styrene elastomer (TPES). The composite material may be flexible or rigid. In the case of rigid composite materials, the mixture may include a thermoplastic resin selected from polyamide 11 (PA), polyamide 10 (PA10), polyamide 610 (PA610), and polyethylene furanoate (PEF) to absorb impact, and a polyurethane (PU) or polyether block amide (PEBA) type thermoplastic elastomer resin. Thus, the thermoplastic elastomer resin is present in a weight percentage of 1-10% based on the total weight of the resin mixture. Rigid composite materials may include several grades of the same type of thermoelastic resin and the same type of thermoplastic elastomer resin, for example, several PA11 resins with different rheologies. Preferably, the PA11, PA10, and PEF resins are 98% bio-based, the PA610 resin is 62% bio-based, and the thermoplastic elastomer resin is more than 40%, more preferably 98% bio-based. In the case of flexible composite materials, only flexible thermoplastic elastomer resins are used.This may be a composite material containing a resin selected from PEBA (polyether block amide), TPC (thermoplastic copolyester elastomer), TPU (thermoplastic polyurethane elastomer), TPO (thermoplastic polyolefin elastomer), TPV (thermoplastic vulcanized elastomer), and TPES (thermoplastic styrene elastomer). As mentioned above, it may also contain several grades of this type of resin, and therefore having different rheologies. Preferably, it is a resin or a mixture of the same type of resin selected from TPU, TPC, and PEBA. - A mineral filler comprising calcium carbonate (CaCO3)-based mineral material and porous silica-based mineral material, wherein the total weight percentage is 25% to 79.9%, preferably 40% to 49.9%. The CaCO3-based mineral material is derived from shellfish, more precisely from shellfish production waste. These are preferably scallop and / or oyster shells because they have a brighter natural color. They are present with a particle size of 100 μm or less, preferably 20 μm or less, and this particle size is measured using laser diffraction (ISO 13220-1 (2009)). The porous silica is derived from diatom skeletons. These are microalgae, which are single-celled organisms with a silica skeleton. The porous silica in the diatom skeleton is farmed and therefore renewable. The porous silica is present in a weight percentage of 2% to 20% of the total weight of the mineral filler. Microporous silica can be doped with other antibacterial additives such as silver ions, gold nanoparticles, or copper oxide nanoparticles to increase its antibacterial effect tenfold. - A dispersant having a weight percentage of 0.1 to 5%, preferably 0.1 to 1%. This may be a natural wax, paraffin, surfactant, etc. -Optionally, a staining system in which the weight percentage is 0% to 5%. For example, the staining system can be formed from one or more bio-based resins concentrated in a natural coloring material such as PA11 resin or PA10 resin. Optionally, the staining system may include shell-derived mineral material having size fractions or combinations of different size fractions taken by sieving, where the average size of these different fractions is larger, between 100 and 500 μm. This allows for the visualization of shell grains when a specific aesthetic effect is desired. The mineral material may be other types of shells such as scallop shells, oyster shells, or mussels, in which case larger particles are selected. The percentage of this mineral material in the staining system can be between 1% and 10%, or between 0% and 0.3%, based on the total weight, with an upper limit of 10%. -Optionally, a reinforcing material, having a weight percentage of 0% to 8%. The reinforcing material can exist in various forms, for example, in the form of fibers or particles. For example, it can be a plant or non-plant-derived metal, mineral or organic fiber. For example, calcium alginate fiber derived from seaweed is preferred. Alternatively, carbon fibers, glass fibers or glass beads can be used. -Optionally, a coupling agent for optimizing the interface between mineral fillers, any reinforcing materials, and resin mixtures. This coupling agent can be present in a weight percentage of 0% to 5%. For example, it may be a copolymer of ethylene and acrylic acid. It may also be a copolymer of ethylene vinyl acetate and acrylic acid.

[0011] The present invention further relates to a method for manufacturing the above-mentioned article, which includes the following steps: - A process for providing porous silica derived from seashells and diatom skeletons, A step of providing a bio-based thermoplastic resin of -1 or more. Preferably, the thermoplastic resin of 1 or more is 30 cm 3 It has a melt volume ratio of less than 10 minutes. - A step of collecting, sorting, washing, crushing, sieving, and retaining particles having a particle size of 100 μm or less, preferably 20 μm or less, of the shell. - A step of mixing the shell particles and the porous silica, wherein the mixture forms a mineral filler. - A step of mixing the mineral filler and one or more thermoplastic resins with a dispersant. - Optionally, a step of adding a dyeing system, a reinforcing material, and / or a coupling agent to the mixture derived from the mineral filler, one or more thermoplastic resins, and the dispersant. - A step of molding the mixture derived from the mineral filler, one or more thermoplastic resins, and the dispersant with any additives to obtain an article.

[0012] The molding can be carried out by injection molding after a prior compounding step by biaxial extrusion and granulation. Alternatively, the manufacturing method can be carried out by extrusion.

[0013] Before crushing, the shells are sorted manually or automatically by color. To remove organic matter, they can be washed by physicochemical washing involving mechanical action such as brushing in a basic solution such as a bleaching agent.

[0014] To improve the compactness of the filler and be able to fill the system with a resin level of 40% or more by weight, preferably, shell particles of different particle sizes are mixed to have a wider particle size distribution or a polymodal particle size distribution. For example 100% of the fraction sieved at 10 μm, 50% of the fraction sieved at 20 μm, and 10% of the fraction sieved at 100 μm can be combined. The fraction with a larger particle size can be optionally recovered for use in a dyeing system to give a specific aesthetic appearance. <Note> Item 1 Articles made from composite materials containing the following by weight: - One or more thermoplastic resins that are at least partially bio-based, the one or more of the above The total percentage of thermoplastic resins is 20% to 74.9%, and one or more thermoplastic resins Fat, - Shell-based mineral materials and porous silica-based mineral materials derived from diatom skeletons A mineral filler having a percentage of 25% to 79%. 9% mineral filler, - A dispersant, wherein the percentage is 0.1% to 5%, preferably 0.1% to 1%. dispersant, -Optionally, a staining system, where the percentage is 0% to 5%. system, -Optionally, a reinforcing material whose percentage is between 0% and 8%. -Optionally, a coupling agent whose percentage is 0% to 5%, Plunging agent. Section 2 The above one or more thermoplastic resins make up 60% or more, preferably 85% or more, overall. Preferably, it is characterized by being 98% or more bio-based, and this percentage is according to standard ASTM standards. The articles described in the preceding paragraph, measured according to D6866-22. Section 3 The one or more thermoplastic resins mentioned above are polyamide 11, polyamide 10, polyamide 610, Polyethylene furanoate, polyurethane, polyether block amide, thermoplastic copolymer Polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyolefin Select from elastomers, thermoplastic vulcanized elastomers, and thermoplastic styrene elastomers. The article described in item 1, characterized by being such. Section 4 In the case of rigid composite materials, it is polyamide 11, polyamide 10, polyamide 610 A thermoplastic resin selected from a first list consisting of polyethylene furanoate and A thermoplastic selected from a second list consisting of polyurethane and polyether block amide. Includes a plastic elastomer resin, or selected from the first and second lists. The article according to the preceding paragraph, characterized in that it contains multiple resins of the same type. Section 5 In the case of flexible composite materials, it is polyether block amide, thermoplastic copolyester Thermoplastic elastomer, thermoplastic polyurethane elastomer, thermoplastic polyolefin elastomer A list consisting of mer, thermoplastic vulcanized elastomers and thermoplastic styrene elastomers. It includes a thermoplastic elastomer resin selected from the above list, or the same selected from the above list. The article according to item 3, characterized by containing multiple resins of the same type. Section 6 The weight percentage of the inorganic filler is 40% to 49.9%, and the heat of 1 or more The article according to item 1, characterized in that the total weight percentage of the plastic resin is 50% to 59.9%. Section 7 The porous silica is present in an amount of 2% to 20% by weight of the mineral filler. The article described in item 1, characterized by the following: Item 8 The article according to claim 1, characterized in that the porous silica is doped with one or more antimicrobial additives. Section 9 The one or more antimicrobial additives are selected from silver ions, gold nanoparticles, and copper oxide nanoparticles. The article described in the preceding paragraph, characterized by the features described herein. Section 10 The aforementioned seashell-based mineral material has a particle size of 100 μm or less, preferably 20 μm or less. The article described in item 1, characterized by doing so. Section 11 The dyeing system further comprises a shell-based mineral material, wherein the mineral material is 10 The article according to item 1, characterized by having a particle size of 0 μm to 500 μm. Section 12 Based on the weight percentage of the dyeing system, the weight percentage of the mineral material is The article described in the preceding paragraph, characterized in that it is 1% to 10%. Section 13 A method for manufacturing the article described in item 1, including the following steps: a. The aforementioned shell-based mineral material and the aforementioned porous silica-based material derived from diatom skeletons. Process of providing mineral materials, b. A step of providing one or more thermoplastic resins that are at least partially bio-based. 、 c. The aforementioned seashells are collected, sorted, washed, crushed, and sieved to a particle size of 100 A process for retaining only shell particles smaller than μm, d. A step of mixing the seashell particles and porous silica, wherein the mixture contains mineral fillers. Forming, process, e. Mix the mineral filler and the one or more thermoplastic resins with the dispersant. To the extent, f. Optionally, the mixture obtained in step e is to be treated with the dyeing system, reinforcing material and / Alternatively, a coupling agent is added, g. A step of molding the mixture obtained in step e or step f to obtain the article. Section 14 The above one or more thermoplastic resins, 30 cm 3 It has a melting volume fraction of less than 10 minutes. A method described in the preceding paragraph, which is characterized by... Section 15 To improve the compactness of the mineral filler, the seashell particles of different sizes are used. The method according to claim 13, characterized in that the mixture is added in step d. Section 16 The method according to item 13, characterized in that the material is washed by mechanical action in a basic solution before crushing. Item 17 The molding step g is characterized by being carried out by injection molding or extrusion molding. The method described in item 13.

Claims

1. An article made of a composite material, wherein the composite material is by weight: - One or more thermoplastic resins that are at least partially bio-based, wherein the total percentage of the one or more thermoplastic resins is 20% to 74.9%, - A mineral filler which is a combination of a seashell-based mineral material and a porous silica-based mineral material derived from a diatom skeleton, wherein the seashell-based mineral material has a particle size of 100 μm or less, and the percentage of the mineral filler is 25% to 79.9%, and - A dispersant, wherein the percentage is 0.1% to 5%. Includes, The aforementioned composite material is by weight: - A staining system in which the percentage is between 0% and 5%. - A reinforcing material selected from the group consisting of calcium alginate fibers derived from seaweed, carbon fibers, glass fibers, and glass beads, wherein the percentage of the reinforcing material is 0% to 8%, and / or - A coupling agent, wherein the percentage is between 0% and 5%. Articles that may further include the following.

2. The article according to claim 1, characterized in that the one or more thermoplastic resins are bio-based in whole, and the proportion is measured according to the standard ASTM D6866-22.

3. The article according to claim 1, characterized in that the one or more thermoplastic resins are selected from polyamide 11, polyamide 10, polyamide 610, polyethylene furanoate, polyurethane, polyether block amide, thermoplastic copolyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyolefin elastomer, thermoplastic vulcanized elastomer, and thermoplastic styrene elastomer.

4. The article according to claim 1, characterized in that, in the case of a rigid composite material, it comprises a thermoplastic resin selected from a first list consisting of polyamide 11, polyamide 10, polyamide 610 and polyethylene furanoate, and a thermoplastic elastomer resin selected from a second list consisting of polyurethane and polyether block amide, or comprises a plurality of resins of the same type selected from the first and second lists.

5. The article according to claim 3, characterized in that, in the case of a flexible composite material, it comprises a thermoplastic elastomer resin selected from the list consisting of polyether block amide, thermoplastic copolyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyolefin elastomer, thermoplastic vulcanized elastomer and thermoplastic styrene elastomer, or comprises a plurality of resins of the same type selected from the list.

6. The article according to claim 1, characterized in that the weight percentage of the inorganic filler is 40% to 49.9%, and the total weight percentage of the one or more thermoplastic resins is 50% to 59.9%.

7. The article according to claim 1, characterized in that the porous silica is present in an amount of 2% to 20% by weight of the mineral filler.

8. The article according to claim 1, characterized in that the porous silica is doped with one or more antimicrobial additives.

9. The article according to claim 8, characterized in that the one or more antimicrobial additives are selected from silver ions, gold nanoparticles, and copper oxide nanoparticles.

10. The article according to claim 1, characterized in that the seashell-based mineral material has a particle size of 20 μm or less.

11. The article according to claim 1, wherein the staining system further comprises a shell-based mineral material, and the mineral material contained in the staining system has a particle size greater than 100 μm and less than or equal to 500 μm.

12. The article according to claim 11, characterized in that, based on the weight percentage of the dyeing system, the weight percentage of the mineral material contained in the dyeing system is 1% to 10%.

13. A method for manufacturing an article according to claim 1, comprising the following steps: a. A step of providing the aforementioned shell-based mineral material and the aforementioned porous silica-based mineral material derived from diatom skeletons, b. A step of providing one or more thermoplastic resins that are at least partially bio-based, c. A step of collecting, sorting, washing, crushing, and sieving the aforementioned seashells to retain only seashell particles with a particle size of 100 μm or less. d. A step of mixing the seashell particles and porous silica, wherein the mixture forms a mineral filler. e. A step of mixing the mineral filler and the one or more thermoplastic resins with the dispersant, or A step comprising mixing the mineral filler and one or more thermoplastic resins with the dispersant, and adding the dyeing system, reinforcing material and / or coupling agent to the resulting mixture, g. A step of molding the mixture obtained in step e to obtain the article.

14. The above one or more thermoplastic resins, 30 cm ３ The method according to claim 13, characterized in that it has a melting volume fraction of less than 10 minutes.

15. The method according to claim 13, characterized in that, in order to improve the compactness of the mineral filler, the seashell particles of different sizes are mixed in step d.

16. The method according to claim 13, characterized in that the material is washed by mechanical action in a basic solution before being crushed.

17. The method according to claim 13, characterized in that the molding step g is carried out by injection molding or extrusion molding.