Materials for timekeeping and jewelry

Abstract

To propose a new aesthetically appealing material for manufacturing timepieces and jewelry. The invention relates to an article, in particular a jewelry or timepiece article, made of a material comprising a matrix (2) of synthetic material containing particles (3) of precious or semi-precious stones, the particles (3) having a d90 particle size measurement of between 50 μm and 2 mm, preferably between 100 μm and 1 mm, more preferably between 150 μm and 500 μm.

Description

Technical Field

[0001] The present invention relates to an article made of a material having a specific aesthetic effect generated due to the dispersion of powder of a semi-precious stone or a precious stone such as diamond in a synthetic matrix. More specifically, the present invention relates to a timepiece or a jewelry item that is wholly or partially made of this material.

Background Art

[0002] Diamond is sometimes used in a dispersed state to impart specific properties to a matrix. Therefore, there are many studies on handling nano-diamonds dispersed in a matrix to improve thermal conductivity and wear resistance. On the other hand, in timepieces, diamonds are cut and set for use to give an aesthetic appearance to the article. To the applicant's knowledge, diamond powder has not been dispersed and used in a matrix to improve the aesthetic appearance of a material. The same applies to other semi-precious stones or precious stones such as rubies. [[ID=NO=30]]

Summary of the Invention

Problems to be Solved by the Invention

[0003] The main object of the present invention is to propose a new aesthetically attractive material for manufacturing timepieces and jewelry items.

Means for Solving the Problems

[0004]

[0005] A synthetic material containing powder of precious or semi-precious stones of micrometer size to achieve the above effect. We provide a material that includes a matrix made of materials.

[0005] Preferably, the particles, for example, diamond particles, are 50 μm to 2 mm in size, preferably It has a diameter d90 of 100 μm to 1 mm, more preferably 150 μm to 500 μm. The particles have the function of strengthening and stabilizing the bond between the particles and the synthetic material. It is covered with a plucking agent.

[0006] Because a coupling agent is present around the particles, the article is reinforced, and over time... It is highly stable, and the dispersion of particles within the synthetic material can be well controlled during manufacturing.

[0007] The coupling agent contains, on the one hand, particles, and on the other hand, organic functional groups of the synthetic material. There must be a reactive functional group for chemical bonding, preferably a coupling agent. , compounds selected from the group consisting of organosilanes, titanates, and zirconates The coupling agent is present in a mixture of synthetic material and particles in an amount of 0.1 to 5% by weight. Preferably, the coupling agent is 3-glycidyloxyepoxypropyl Trimethoxysilane (3-glycidyloxy epoxy propyltrimethoxysilane), pyrophosphate Pyrphosphatotitanate and isopropyltri[di(octyl)phosphatitanate] Isopropyl tri[di(octyl)phosphato] titanate or tetra-n - Select from the group consisting of zirconium tetra-n-propanolate. It is done.

[0008] Preferably, especially in the case of diamond powder, d90 is 150 μm or more, and this enhances the glittering effect of the diamond.

[0009] The application field varies depending on the hardness of the matrix. Therefore, a flexible matrix is preferred for the production of bracelets, and a hard matrix is preferred for the production of trim parts and movement parts. Preferably, a hard matrix is used for the production of trim parts and movement parts.

[0010] The appearance can be adjusted according to the type of stone, particle size, and content rate in the matrix. Therefore, it is possible to increase or decrease the visibility of a wide range of colors and the particles constituting the powder, obtain a more or less remarkable sparkling effect, or a depth effect according to the light transmittance level of the matrix.

[0011] In addition, with this new material, it is possible to recycle the scraps generated by cutting diamonds, precious stones, and semi-precious stones, especially those used in the field of timepieces.

[0012] Other advantages will also become apparent from the features expressed in the claims and from the following detailed description of the present invention given by way of example while referring to the drawings. And it is not limited to this.

Brief Description of the Drawings

[0013] [Figure 1] It is a schematic diagram of a portable timepiece (e.g., a wristwatch, a pocket watch) equipped with a bracelet made of the material according to the present invention.

Modes for Carrying Out the Invention

[0014] The present invention relates to timepieces, and more particularly to timepieces or jewelry made of composite materials. An article means both a small element intended to be fixed to a base material, such as a decorative element ( logo, etc.), and a large structural element.

[0015] The material for application to the bracelet 1 shown in FIG. 1 includes a synthetic matrix 2 containing powders 3 of precious stones such as diamonds, rubies, sapphires and emeralds, or semi-precious stones such as quartz, topaz, garnet also known as fine stones, or organic stones such as nacre and amber. The precious stones or semi-precious stones include both natural stones and synthetic stones. As an example, specifically, an example related to diamond powder will be used for explanation.

[0016] According to the present invention, the powder is on the micrometer scale. The particle size of the powder is measured by laser diffraction in accordance with ISO 13 320:2009 and is represented hereinafter by diameter d10 and d 90. d10 and d90 respectively mean that 10% and 90% (number) of the particles have a given diameter or less (cumulative distribution). Preferably, the particle size measurement value d9 0 is 50 μm to 2 mm, more preferably 100 μm to 1 mm, still more preferably 150 μm to 500 μm. If the distribution of the d90 particle size measurement value is below 150 μm, the particles will not have a glittery appearance and will not be recognized as precious particles. However, if the particle size is finer, more diamonds can be dispersed in the resin to obtain a material with a large carat number. These powders preferably have a fine particle size of 1 μm to 100 μm, more preferably 20 μm to 50 μm, still more preferably 1 to 20 μm. ​​​​ It has a cloth-like structure (better dispersibility), the cumulative distribution d90 is 5-15 μm, and d10 is 3-5 It is μm.

[0017] Diamonds can be of natural origin, and this is why they produce purple light at 365nm. Certain particles fluoresce under external irradiation. Because they are of natural origin, the powder It gives a glossy, creamy appearance. Also, the diamond is a synthetic diamond. It is also possible to produce a single crystal that gives a lustrous powder with a golden appearance. Furthermore, the powder can be a polycrystalline material exhibiting a glossy black color.

[0018] Preferably, the matrix is ​​light-transmitting so that the particles within the matrix can be visualized. It is made from transient base resin. Depending on the particle content, this resin can become opaque to light. The possibility increases. However, even if the particles are close to the surface of the material, their size is sufficient. As long as it is, it can still give a certain sheen.

[0019] The matrix can be flexible or rigid, depending on the article being made. It is possible.

[0020] A flexible matrix is ​​a Shore A matrix of 80 or less (ISO 7619-1:20 10) A matrix having hardness, and such a flexible matrix is ​​called The bracelet is overmolded to give it a "soft touch" look. To manufacture flexible parts such as bezels and crowns Select for manufacturing decorations. The matrix is ​​a light-transmitting elastomer that provides the elastic properties required for the application. This is the matrix. Preferably, the elastomer is selected for its resistance to the passage of time. Based on light-transmitting fluorinated elastomers (FKM, FFKM) that are known to be effective. However, thermovulcanizable silicone (EVC), polyurethane elastomer (PU) Select R) or other light-transmitting elastomers such as thermoplastic elastomers (TPE). It is also possible.

[0021] The powder content is adjusted to maintain the flexibility of the material. Therefore, the powder The amount of the topping is 0.5 to 40% by weight, preferably 0.5 to 30% by weight, relative to the total weight of the material. It contains 1-5% by weight. A content of 5% or less dramatically alters the mechanical properties. It becomes possible to maintain the light transmittance of the material without changing its properties. When maintained, the depth effect with the material at the bottom of the case when using composite materials as decorative elements Such optical effects can be achieved. Furthermore, by maintaining the properties of the substrate, Suitable for use in overmolding bracelets or decorating timepieces. This can be made certain.

[0022] Tests were conducted on the base resin FFKM (grade 5910M) obtained from Solvay. And this test was successful. By mixing in an open mixer (calendering) Diamond powder with a d90 of 50 μm was dispersed within the elastomer. - Without changing the characteristics and viscosity of single-crystal and polycrystalline natural or synthetic diamonds The powder is dispersed to contain 2.5% by weight, and finally, the desired purity is obtained in the resulting product. We were able to create a flipping effect.

[0023] Furthermore, single-crystal and polycrystalline natural or synthetic diamond powders with a d90 of 60 μm are also available. Additional tests were conducted using RTV (room temperature vulcanization) silicone containing 30% by weight. The procedure was performed. No cracks were observed in the elastomer. Finally, the diamond powder was incorporated. Due to its high prevalence, the product is opaque to light. Nevertheless, this product is attractive. It has a beautiful appearance. By adding diamond powder to make it 30% by weight, the material's texture is improved. A increased by 10 points, but nevertheless it was always below 75 points, typically Shore A scores 60-70 points. This is a desirable value for bracelet comfort. Oh, if the content is this high, the hardness of the diamond will damage the mixer rollers. There is a tendency for this to happen. This is industrially undesirable. In this case, heat-vulcanizable gills It is preferable to pre-disperse microdiamonds in the stomer solution. By evaporating the medium, FKM fine particles containing microdiamonds were obtained.

[0024] Instead of the flexible matrix described above, a rigid / hard matrix is ​​used. Replace the case middle section, case bottom, bezel, press parts, bracelet links, and dial. , hands, trim parts such as the index on the dial, or parts such as bridges and plates It can manufacture movement parts. A "hard matrix" has a Shore D hardness of 8. This refers to a matrix that is greater than or equal to 0 (ISO 868:2003).

[0025] In the case of a rigid matrix, even if the hardness increases after the addition of diamond, flexibility remains It does not have a more significant impact than in the case of a matrix. Therefore, the powder content is considerably large. Therefore, the content can be increased to more than 50% by weight. Thus, the weight percentage is, The content is 0.5-90%, preferably 5-80%, more preferably 30-70%. The selection is made according to the level of light transmittance, the desired viscosity of the resin, and the desired final result. Trix is ​​a light-transmitting resin, such as acrylic resins or polyurethanes. It consists of a polymer resin system, an epoxide system, or a copolymer resin system that combines monomers of these systems. It can be a thermosetting resin selected from the group. Furthermore, the selection of the resin is similar to PMMA. Acrylic thermoplastic resin may be selected, or polycarbonate (PC) thermoplastic resin may be used. A resin may be selected. According to the present invention, before adding the curing agent, diamond powder is used. It is pre-dispersed within the resin. The hardener is added before the resin is poured into the mold. Therefore, We can manufacture inserts like all kinds of logos and decorations, and these will then For example, by overmolding, bonding, welding, riveting or screwing, trim It is assembled into parts. It is also possible to directly mold the timer, and its mechanical characteristics The result depends primarily on the selected resin and diamond content. It is also machined and pressed. Powder is deposited into the housing, which is made of parts such as the bezel and sapphire glass, using a syringe. It is also possible to inject a resin containing the powder. The resin is deposited inside the housing, Once cured, excess resin is removed by sanding. The arrangement in this article is epoxy Good fluidity of such resins (<1000 mPa·s) -1 ) is promoted by, typically 8 It can be cured at a low temperature of 0°C.

[0026] Shore hardness 90D epoxyamine type two-component light-transmitting thermosetting resin (refractive index) The test was conducted using 1.5). The coupling between the microdiamond and the epoxy resin As a glycerin agent, we use the epoxysilane (3-glycidyl iodine) of the Dynasylan Glyeo (registered trademark) brand. Using xyepoxypropyltrimethoxysilane, 60% by weight of microdiamonds The d90 was dispersed in epoxy resin. Regarding diamonds, using single-crystal and polycrystalline natural and synthetic microdiamonds The test was conducted. In the case of natural diamonds, the product has a luster that is more or less depending on the particle size. It had a creamy appearance. In the case of synthetic single-crystal diamond, the product varies depending on the grain size. It had a more or less glossy, golden appearance. In the case of synthetic polycrystalline diamonds, The organism had a black appearance. Also, the ruby ​​stone of the timer with the chemical formula Al2O2Cr was crushed and d9 Obtain scrap with a diameter of 500 μm and add a light-transmitting epoxy resin to contain 60% by weight. Further tests were conducted using a material dispersed in lipids. Visible lumens were observed within the matrix. We observed the beautiful color effect caused by the presence of bee particles.

[0027] In summary, depending on the type, size, and proportion of stones within the matrix, a wide range of factors are involved. It can be seen that the following effects (color, gloss, light transmittance, visibility of powder particles) can be obtained. Later, coloring, fluorescent, and / or phosphorescent materials are added to a (flexible or rigid) matrix. In addition, it should be clearly stated that the aesthetics of the items can be adapted as needed.

[0028] In an alternative embodiment, the matrix can be opaque to light, in this case Stone particles having a size of 100 to 500 μm are preferred. Naturally, by injection molding, etc. The resulting material can be polished to reveal stone particles on its surface.

Claims

1. An article for decorative purposes made of a material comprising a matrix (2) of a synthetic material containing particles (3) of precious or semi-precious stones, The particle size distribution of particle (3) is 1 to 50 μm, with d90 being 5 to 15 μm and d10 being 3 to 5 μm. The particles are covered with a coupling agent that has the function of strengthening the bond between the particles and the synthetic material. The aforementioned particles (3) are particles of diamond, emerald, sapphire, or ruby ​​of natural or synthetic origin. An article characterized by the following:

2. The coupling agent is a compound selected from the group consisting of organosilanes, titanates, and zirconates. The article according to feature 1.

3. The coupling agent is contained in a mixture of synthetic material and particles in an amount of 0.1 to 5% by weight. The article according to any one of claims 1 to 2.

4. The coupling agent is selected from the group consisting of 3-glycidyloxyepoxypropyltrimethoxysilane, pyrophosphate titanate, isopropyltri[di(octyl)phosphate] titanate, and zirconium tetra-n-propanolate. The article according to any one of the features 1 to 3.

5. The diamond is of natural origin to give the material a creamy color, a synthetic single crystal to give the material a golden color, or a synthetic polycrystalline to give the material a black color. The article according to any one of the features 1 to 4.

6. The matrix (2) further includes coloring, fluorescence and / or phosphorescence materials. The article according to any one of claims 1 to 5.

7. Forming movement or trim components used in the manufacture of timekeeping devices. The article according to any one of claims 1 to 6.

8. The movement component or trim component is made from the material. The article according to feature 7.

9. The aforementioned movement component or trim component comprises a portion made of the aforementioned material, The aforementioned portion is assembled onto the surface of the article or housed in a recess formed within the article. The article according to feature 7.

10. The aforementioned part is a logo, decoration, or element. The article according to feature 9.

11. Articles made of a material containing a rigid matrix, used as movement components or trim components of a timepiece, selected from the group consisting of bracelet links, clasps, case middles, press parts, crowns, bezels, crystals, dials, hands, dial indices, case bottoms, plates, wheels, and bridges. The article according to any one of claims 7 to 10, characterized by the features described herein.

12. Made from a material containing a flexible matrix, The bracelet (1) is the trim component. The article according to any one of claims 7 to 10, characterized by the features described herein.

13. The matrix (2) is a flexible matrix, The material includes a flexible matrix having a Shore A hardness of 80 or less. The article according to any one of claims 1 to 10 and 12.

14. The matrix (2) of the synthetic material is made of a light-transmitting elastomer resin selected from the group consisting of fluorinated elastomers, thermovulcanizable silicones, polyurethane elastomers, and thermoplastic elastomers. The article according to feature 13.

15. The content of the aforementioned particles (3) is 0.5 to 40% by weight. The article according to feature 13 or 14.

16. The matrix (2) is a rigidity matrix, The material includes the matrix (2) having a Shore D hardness of 80 or higher. The article according to any one of claims 1 to 11.

17. The content of the aforementioned particles (3) is 0.5 to 90% by weight. The article according to feature 16.

18. The matrix (2) of the synthetic material is made of a light-transmitting thermoplastic resin of acrylic or polycarbonate, or a light-transmitting thermosetting resin selected from the group consisting of copolymers of acrylic, polyurethane, epoxide, and combinations of monomers of these systems. The article according to feature 16 or 17.

19. The article comprises the article described in any one of claims 7 to 18. A portable watch characterized by the following features.

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