Synthetic stone and method of forming synthetic stone

Abstract

This invention relates to synthetic stone. This invention also relates to a method for forming synthetic stone.

Description

Technical Field

[0001] This invention relates to synthetic stone. This invention also relates to a method for forming synthetic stone. Background Technology

[0002] Circular quartz is a mineral obtained by calcining pure quartz sand at a temperature of about 1550°C (for example, at a temperature of 1300°C to 1700°C).

[0003] At room temperature, quartz sand is primarily composed of a mineral phase called α-quartz. When α-quartz is heated to approximately 1550°C, its crystal lattice undergoes a phase transition. Upon heating, α-quartz first undergoes a phase transition to form β-quartz. With further heating, β-quartz forms tridymite, and then at even higher temperatures (typically 1300°C to 1700°C at atmospheric pressure), it forms cristobalite.

[0004] Quadrilateral quartz is chemically stable and has high mechanical strength. Commercially available quadrilateral quartz also has a high whiteness. Due to its ease of processing, quadrilateral quartz is widely used in various fields. For example, it is used in engineered stone (such as work surfaces) and coatings.

[0005] In the engineered stone market (sometimes abbreviated as EGS), one of the largest markets for cubic quartz is the production of kitchen countertops (e.g., in the form of synthetic stone). These countertops consist of mineral fillers and resins. Countertops typically contain a high proportion (up to 92% by weight) of mineral fillers, along with one or more resins present in a lower percentage (optionally: 2K epoxy resin, such as Fugante™ Epoxy 2K; or polyester resin, such as POLARIS polyester resin (manufactured by Ashland™)). Cubic quartz, quartz, or a combination of both are typically integrated into the countertop as mineral fillers.

[0006] Typically, countertops (composed of mineral fillers and resin) need to be cut before installation. Countertops are usually dry-cut using simple grinding tools. This method of cutting countertops generates dust consisting of a mixture of resin and mineral fillers. This mineral dust may contain cristobalite, quartz, or a combination of cristobalite and quartz. Inhalation of cristobalite and quartz dust can cause occupational silicosis.

[0007] The carcinogenic properties of cristobalite and quartz have been studied when they are dispersed in the air and inhaled. The most dangerous particles are those with a diameter of less than 10 µm, as well as particles newly generated during high-energy cutting processes.

[0008] Typically, synthetic stone used in the EGS market is made in white or off-white. Sometimes, it is desirable to add black and / or gray and / or other colored materials to the synthetic stone. For example, sometimes it is desirable to add black and / or gray and / or other colored textures to synthetic stone that is originally white or off-white.

[0009] There is a need for a beneficial synthetic stone. In particular, there is a need for a synthetic stone that does not contain quartz, quartz, or a mixture of quartz and cristobalite; or, there is a need for a synthetic stone in which quartz, quartz, or a mixture of quartz and cristobalite is reduced to less than 1% by weight. Summary of the Invention

[0010] This invention relates to a synthetic stone that contains little or no quartz, quartz, or a mixture of quartz and cristobalite.

[0011] This invention relates to a discovery that waste glass (e.g., chopped glass) containing little or no crystalline silica (i.e., less than 1% by weight of silica) can be used in the production of synthetic stone. This synthetic stone exhibits chemical and mechanical properties similar to synthetic stone formed from quartz and / or cristobalite, while containing little or no silica (i.e., less than 1% by weight of crystalline silica). Adding waste glass (e.g., chopped glass) to synthetic stone also allows for the formation of synthetic stones in a variety of colors, making them suitable for synthetic stone production.

[0012] The inventors have discovered that using waste glass in synthetic stone provides at least the following benefits: - Reduce the total carbon footprint of synthetic stone (compared to using new, non-recycled materials).

[0013] - Reduce the total content of crystalline silica.

[0014] - Maintain the high transparency of synthetic stone, thus preserving its aesthetic appeal.

[0015] The waste glass used in this invention can come from one or more of the following waste glass streams: i. Container glass and / or tableware glass ii. Float glass iii. Pharmaceutical (medicinal) glass iv. Photovoltaic (PV) glass v. To insulate glass (e.g., glass wool). vi. Reinforcing glass fiber vii. LCD glass According to the present invention, the waste glass contained in the synthetic stone: - It can be white or near-white, and transparent or semi-transparent.

[0016] - It can have good chemical resistance.

[0017] - It can have a suitable porosity of less than or equal to 6%.

[0018] This invention is set forth in the following terms: 1. A synthetic stone comprising: Waste glass, and Adhesive.

[0019] 2. The synthetic stone described in Clause 1, wherein the waste glass is shattered glass.

[0020] 3. The synthetic stone described in Clause 1 or 2, wherein the waste glass comprises or is composed of the following substances: i. Container glass with the following chemical composition:

[0021] and / or; ii. Float glass with the following chemical composition:

[0022] and / or; iii. Pharmaceutical (medical) glass having the following chemical composition:

[0023] And / or, iv. Photovoltaic (PV) glass with the following chemical composition:

[0024] and / or

[0025] v. Insulating glass (e.g., glass wool) having the following chemical composition:

[0026] and / or

[0027] vi. Low-alkali glass fibers with the following chemical composition:

[0028] And / or, vii. Borosilicate glass fibers with the following chemical composition:

[0029] And / or, viii. LCD glass with the following chemical composition:

[0030] UI refers to unavoidable impurities.

[0031] 4. The synthetic stone according to any one of clauses 1 to 3, wherein the synthetic stone comprises: 1 to 90% by weight, or 1 to 70% by weight, or 1 to 40% by weight, or 1 to 30% by weight of waste glass; or, 2 to 90% by weight, or 2 to 70% by weight, or 2 to 40% by weight, or 2 to 30% by weight of waste glass; or, 5 to 90% by weight, or 5 to 70% by weight, or 5 to 40% by weight, or 5 to 30% by weight of waste glass.

[0032] 5. The synthetic stone according to any one of clauses 1 to 4, wherein the waste glass is in granular form; optionally, wherein the granules are: The particle size ranges from 1.0 to 0.063 mm (fine particles), or the particle size is less than 63 micrometers (micro powder); and / or, The particle size D90 is less than 50 micrometers, or less than 40 micrometers, or between 10 and 40 micrometers.

[0033] 6. The synthetic stone according to any one of clauses 1 to 5, wherein the adhesive comprises or is composed of resin; optionally, wherein the synthetic stone comprises 6 to 20% by weight of resin; optionally, The resin is an epoxy resin, a polyester resin, or a polyurethane resin; optionally, the resin is a 2K epoxy resin.

[0034] 7. The synthetic stone of any one of Clauses 1 to 6, wherein the synthetic stone further comprises pigments, silanes, catalysts, accelerators or mixtures of any two, three or four of these components.

[0035] 8. The synthetic stone according to any one of clauses 1 to 7, wherein the synthetic stone comprises: Less than 1% by weight of crystalline SiO2, or less than 0.5% by weight of crystalline SiO2, or less than 0.1% by weight of crystalline SiO2, or no crystalline SiO2; and / or, Less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.01% by weight of cristobalite, quartz, or cristobalite and quartz; and / or, Trace amounts (less than 1% by weight, or less than 0.5% by weight, or less than 0.01% by weight) of wollastonite, diopside, calcium magnesium silicate, mica and / or sphene.

[0036] 9. The synthetic stone according to any one of clauses 1 to 8, wherein the waste glass is: a. White or near-white; b. Transparent or semi-transparent; c. For chemical resistance; and / or, d. Has an open area ratio of less than or equal to 6%.

[0037] 10. A coating composition; or, an ink composition; or, a filter medium; or, a ceramic composition; or, a dental composition; or, a biomedical composition; or, an implant material; or, a fuel cell; or, a nuclear waste solidification composition; comprising the synthetic stone described in any one of clauses 1 to 9.

[0038] 11. A method for forming synthetic stone, optionally the synthetic stone according to any one of clauses 1 to 9, the method comprising the following steps: Provide waste glass, Mix waste glass with adhesive, and The mixture is hardened to form synthetic stone.

[0039] 12. The method described in Clause 11, wherein the method further comprises: In the mixing step, pigments are added to obtain the desired color of the synthetic stone; and / or, In the mixing step, one or more components selected from a list consisting of pigments, silanes, catalysts, accelerators, or mixtures of any two, three, or four of these components are added.

[0040] 13. The method described in Clause 11 or Clause 12, wherein: The waste glass is as described in any one of clauses 2, 3, or 9; and / or, The adhesive is as described in Clause 6.

[0041] 14. Use of waste glass combined with adhesives in the production of synthetic stone; optionally, said synthetic stone is described in any one of clauses 1 to 9. Detailed Implementation

[0042] Some embodiments of this disclosure will be discussed in detail below to illustrate all its features. The words “comprising,” “having,” “containing,” and “including,” and other forms thereof, have the same meaning and are open-ended, meaning that none of the items following these words are intended to be an exhaustive list or to be limited to the one or more items listed.

[0043] It should also be noted that, unless the context clearly specifies otherwise, the singular forms “a,” “an,” and “described” used herein and in the appended claims include the plural designation. While any products and methods similar to or equivalent to those described herein may be used in practice or testing of the embodiments of this disclosure, only preferred products and methods are described herein.

[0044] The embodiments disclosed herein will be described in more detail below. However, the embodiments of the claims may be implemented in many different forms and should not be construed as limited to the embodiments described herein. The embodiments described herein are not limiting examples, but merely examples among other possible examples.

[0045] The following are some terms used to describe this invention: "Silica-free" means a composition containing less than 1% by weight of crystalline silica. The standard method for measuring the crystalline silica content in a composition is X-ray diffraction ("XRD"). Depending on the measuring equipment used, XRD can be accurate to approximately 1% by weight of the crystalline phase. Therefore, a composition "silica-free" means containing less than 1% by weight of crystalline silica. Some XRD measuring equipment can achieve an accuracy of 0.1% by weight, and this level of accuracy can be used to measure whether a composition is silica-free.

[0046] The “CIELAB color space” refers to the color space defined by the International Commission on Illumination (ICI). It uses three values ​​to represent color: L (luminance); a (green-red component); and b (blue-yellow component).

[0047] "Scrap glass" refers to waste glass that has been broken and / or ground. Scrap glass can be classified into different waste streams based on particle size and / or contaminants. Scrap glass may contain organic matter, metals, and / or ceramic fragments.

[0048] "Glass fiber" refers to the glass fibers used in the manufacture of fiber-reinforced plastics. Glass fibers can be randomly arranged, pressed into sheets, or woven into glass cloth. The plastic matrix can be a thermosetting polymer matrix (such as epoxy resin, polyester resin, or vinyl ester resin) or a thermoplastic polymer matrix.

[0049] Glass is an amorphous, non-crystalline solid material. It is typically brittle and usually optically transparent. Glass is defined as an inorganic melt that, upon cooling after its glass transition, reaches a solid state without crystallization. The main component of most commonly used glasses is silicon dioxide (SiO2). Ordinary glass is usually produced using a two-step process, followed by shaping to suit various applications. The first step is batch mixing. The various components that make up glass (typically including at least silicon dioxide, sodium carbonate, calcium carbonate, and recycled glass (in the form of chopped glass), along with small amounts of various other trace components) are mixed to ensure homogeneous mixing and then fed into a furnace. The second step involves heating the mixture to approximately 1500°C, at which point the components melt, undergo various chemical reactions, and release CO2 and SO2. These chemical reactions form molten glass (or "glass solution"), which can be shaped and cooled.

[0050] "White" refers to the color represented using CIELAB color space coordinates. The parameters for white are: 100 (L), 0 (a), 0 (b).

[0051] "Near white" refers to a color represented using CIELAB color space coordinates. The CIELAB color space coordinates for near white are: 90 to below 100 (L), -0.5 to +0.5 (a), and 0 to 4 (b).

[0052] "LOI" refers to Loss on Ignition. This measurement method involves intensely heating a mineral sample at a specific temperature, causing any volatile substances to escape. This process continues until the mineral content no longer changes. The LOI value represents the mass of water and volatile substances in the sample.

[0053] "Weight %" refers to the percentage by weight (in grams) of a component in 100 grams of a composition. For example, if a mineral composition contains 25% by weight of quartz, then 100 grams of the mineral composition contains 25 grams of quartz.

[0054] "Unavoidable impurities" refer to components present in the composition that do not affect the properties of the composition. The content of unavoidable impurities in the composition is: less than 30% by weight; or less than 25% by weight; or less than 20% by weight; or less than 15% by weight; or less than 10% by weight; or less than 5% by weight; or less than 4% by weight; or less than 3% by weight; or less than 2% by weight; or less than 1% by weight; or less than 0.5% by weight; or less than 0.1% by weight. In certain tables of this specification, "UI" is used to refer to unavoidable impurities.

[0055] Synthetic stone

[0056] According to various aspects of the invention, waste glass (e.g., shattered glass) provides favorable properties for use as a substitute for quartz in the manufacture of synthetic stone. Waste glass (e.g., shattered glass) has a wide range of color characteristics, and when mixed with resin, its color does not deviate significantly from that of a mixture of the same resin and high-quality quartz particles (of similar or identical color).

[0057] Compared to other feldspar, quartz, or cristobalite particles, waste glass (such as broken glass) does not contain crystalline silica, thus avoiding the toxicological risks of inhaling inhalable crystalline silica during or after processing into synthetic stone.

[0058] These characteristics, coupled with the high availability of waste glass (e.g., broken glass), enable the waste glass (e.g., broken glass) in this invention to replace quartz particles, thereby overcoming the current disadvantages without requiring major modifications to existing formulations and / or production processes, and without reducing product performance and appearance.

[0059] The use of recycled glass in synthetic stone offers at least the following benefits: - Reduce the total carbon footprint of synthetic stone (compared to using new, non-recycled materials).

[0060] - Reduce the total content of crystalline silica.

[0061] - Maintain the high transparency of synthetic stone, thus preserving its aesthetic appeal.

[0062] According to the present invention, the waste glass contained in the synthetic stone: - It can be white or near-white, and can be transparent or semi-transparent.

[0063] - It has good chemical resistance.

[0064] - It has a suitable porosity with an open area ratio of less than or equal to 6%.

[0065] In this application, waste glass (e.g., broken glass) can be in the form of "particles". "Particle" refers to a single unit (particle). Therefore, the term covers a wide range of units, from tiny powder particles at the micrometer level to larger agglomerates of matter at the millimeter level. The term covers particulate products of various shapes and sizes, including fine particles, fine powders, powders, or combinations thereof.

[0066] The particle size (also known as particle diameter) can be measured by sieving using sieves with different mesh sizes. As used herein, the term "particle size" refers to the range of diameters of individual particles in waste glass (e.g., briquette). It can be measured by the retention or passage of particles on a calibrated sieve with a measured mesh size opening, where a particle either passes through (and is therefore smaller than) a particular sieve or is retained (and is therefore larger than) a particular sieve whose opening size is measured and known. Particle size is defined as the range of particle sizes that a particle can pass through a sieve with a larger mesh opening or "hole" but cannot pass through another sieve with a smaller mesh opening. For waste glass (e.g., briquette) with a particle size < 800 micrometers, the particle size distribution of a sample can be measured using laser diffraction with commercially available equipment (e.g., a Malvern Panalytical Mastersizer 3000 equipped with a hydraulic tank). During measurement, the particle sample can be dispersed in deionized water using an ultrasonic probe. Laser diffractometers can provide particle size distribution curves (particle volume vs. particle size) as well as the D10, D50 and D90 statistical values ​​of the sample particle population (corresponding to the particle size values ​​of 10%, 50% or 90% of the sample particle population below these values, respectively).

[0067] Particle composition can be obtained by X-ray fluorescence spectroscopy (XRF), a technique widely used in the field of mineralogy. The particle composition described herein preferably corresponds to the average value of the composition of a sample containing a certain mass of particles (e.g., 1 gram of particles) (this average value is calculated by repeating the measurement at least three times).

[0068] Different types of waste glass used in the synthetic stone of this invention include, but are not limited to: i. Container glass and / or tableware glass (from recycled container glass).

[0069] ii. Float glass (from recycled window glass and flat glass).

[0070] iii. Pharmaceutical (medicinal) glass (borosilicate glass derived from recycled pharmaceutical glass).

[0071] iv. Photovoltaic (PV) glass (from recycled photovoltaic glass).

[0072] v. Insulating glass (e.g., glass wool) (from recycled insulating glass wool).

[0073] vi. Reinforcing glass fiber (from recycled composite materials or other sources of waste glass fiber).

[0074] vii. LCD glass (from recycled LCD screens).

[0075] The synthetic stone of the present invention may contain (where UI = unavoidable impurities): i. Container glass with the following chemical composition:

[0076] and / or; ii. Float glass with the following chemical composition:

[0077] and / or; iii. Pharmaceutical (medical) glass having the following chemical composition:

[0078] And / or, iv. Photovoltaic (PV) glass with the following chemical composition:

[0079] and / or

[0080] v. Insulating glass (e.g., glass wool) having the following chemical composition:

[0081] and / or

[0082] vi. Low-alkali glass fibers with the following chemical composition:

[0083] And / or, vii. Borosilicate glass fibers with the following chemical composition:

[0084] And / or, viii. LCD glass with the following chemical composition:

[0086] The desired particle size range (particle size analysis) for waste glass (e.g., cullet) can be obtained by grinding and sieving, using methods known in the art, such as grinding with ball mills, grinding rollers, or jaw crushers. Grinding may include micronizing the minerals to obtain refined waste glass (e.g., cullet) particles with an average particle size D90 of less than 50 micrometers, optionally less than 40 micrometers, or optionally D90 of 10 to 40 micrometers.

[0087] In some aspects, the present invention relates to the manufacture of synthetic stone using waste glass (e.g., broken glass) particles. Compared to synthetic stone containing quartz and / or cristobalite, this use can reduce (and possibly even reduce to zero) the emission of crystalline silica during the manufacture or mechanization of synthetic stone. While it is ideal to reduce the crystalline silica content in the claimed synthetic stone to zero, in some aspects, the crystalline silica content is higher, for example, less than 5% by weight, or less than 10% by weight, or less than 25% by weight, or less than 50% by weight.

[0088] Another aspect of the invention relates to a synthetic stone comprising an inorganic filler and a hardening binder, wherein the inorganic filler comprises refined waste glass (e.g., shattered glass) of the present invention.

[0089] The amount of waste glass (e.g., broken glass) particles in synthetic stone is preferably 2 to 70% by weight, or 2 to 50% by weight, or 2 to 30% by weight of the total weight of the synthetic stone. In some aspects, the amount of waste glass (e.g., broken glass) tailings particles in synthetic stone is at least 2% by weight, or at least 4% by weight, or at least 10% by weight, and / or at most 90% by weight, or at most 70% by weight, or at most 50% by weight, or at most 30% by weight of the total weight of the synthetic stone.

[0090] The synthetic stone may also contain inorganic fillers different from the waste glass (e.g., broken glass) particles of the present invention, preferably selected from stone, stone-like materials, or ceramic materials. Other inorganic fillers in the synthetic stone may include synthetic inorganic particles, such as recycled silicate glass particles, silicate frit particles, ceramic particles, or mixtures thereof. Optionally, the inorganic filler (i.e., the sum of the weights of waste glass (e.g., broken glass) and other inorganic fillers) accounts for at least 70% by weight, or at least 80% by weight, or at least 85% by weight, and at most 95% by weight of the total weight of the synthetic stone.

[0091] Synthetic stone with low crystalline silica content is preferred. Therefore, preferably, all or at least 90% by weight, or at least 95% by weight, or at least 99% by weight of the inorganic filler have a low crystalline silica content. Preferably, the crystalline silica (quartz, cristobalite, or other crystalline polymorphs) content is 0 to 15% by weight, or 0 to 10% by weight, or 0 to 7% by weight relative to the weight of the inorganic filler. Preferably, at least 95% by weight, more preferably at least 99% by weight, of the other inorganic fillers in the synthetic stone have a crystalline silica content of 0 to 10% by weight relative to the weight of the inorganic filler.

[0092] In some aspects, the synthetic stone contains no more than 5% by weight or no more than 1% by weight of inorganic filler relative to the weight of the synthetic stone, wherein the inorganic filler has a crystalline silica content of no more than 15% by weight or no more than 10% by weight relative to the weight of the inorganic filler. Preferably, the synthetic stone contains 0 to 5% by weight of inorganic filler relative to the weight of the synthetic stone, wherein the inorganic filler has a crystalline silica content of 15 to 100% by weight relative to the weight of the inorganic filler.

[0093] In some aspects, the synthetic stone does not contain inorganic particles with a crystalline silica content exceeding 15% by weight or 10% by weight. In these aspects, in addition to waste glass (e.g., broken glass) particles as claimed in the claims, the synthetic stone also contains synthetic inorganic particles selected from recycled silicate glass particles, silicate frit particles, ceramic particles, or mixtures thereof. In some aspects, the synthetic stone of the present invention comprises waste glass (e.g., broken glass) particles and silicate glass particles (recycled, frit) with a crystalline silica content of less than 1% by weight, preferably, the sum of the weights of the waste glass (e.g., broken glass) and the silicate glass particles accounts for more than 50%, 70%, or 90% by weight of the total weight of the synthetic stone.

[0094] In some respects, the crystalline silica content of the synthetic stone material is less than or equal to 15% by weight, or less than or equal to 10% by weight, or less than or equal to 5% by weight relative to the weight of the synthetic stone. The crystalline silica content of the synthetic stone material can be 0 to 15% by weight, or 0 to 10% by weight, or 0 to 5% by weight relative to the weight of the synthetic stone.

[0095] In some respects, the waste glass (e.g., broken glass) particles contained in the synthetic stone have a particle size D90 of less than 50 micrometers, or less than 40 micrometers, or a D90 of 10 to 40 micrometers.

[0096] Optionally, the synthetic stone of the present invention may contain only waste glass (e.g., broken glass) particles with a particle size of less than 0.1 mm. In some cases, the amount of waste glass (e.g., broken glass) particles with a particle size of less than 0.063 mm in the synthetic stone is 10% to 40% by weight of the total weight of the synthetic stone.

[0097] The weight of inorganic fillers (the total weight of waste glass (e.g., broken glass) particles and / or any other inorganic particles) in artificial stone products is optionally 70 to 95% by weight, or 85 to 95% by weight, relative to the weight of the synthetic stone.

[0098] The curable adhesive is optionally a curable organic resin, more preferably an organic thermosetting resin, which is preferably a liquid and can be selected from unsaturated polyester resins, methacrylate resins, vinyl resins and epoxy resins. These curable organic resins are preferably reactive and can be cured by a curing (or crosslinking) reaction.

[0099] Depending on some aspects, synthetic stone is produced using a vacuum vibration compaction method, and its apparent density ranges from 2000 to 2600 kg / m³ or 2100 to 2500 kg / m³. The apparent density of synthetic stone can be measured according to EN 14617-1:2013 or any other method known in the art.

[0100] Synthetic stone can be available in the form of square blocks, slabs, standard sheets, thin sheets, plates, or flat panels. It can be used in construction or decoration, such as for countertops, kitchen countertops, sinks, shower trays, wall or floor cladding, stairs, etc.

[0101] The present invention also relates to a method for forming synthetic stone, the method comprising: a) Mix a curable adhesive with an inorganic filler containing waste glass (e.g., broken glass); b) The unhardened mixture obtained in step a) is vacuum vibrated and compacted in a mold; and c) Harden the compacted mixture obtained in step b).

[0102] In the manufacture of synthetic stone, a hardenable binder (e.g., a liquid organic resin) is mixed with waste glass (e.g., sharded glass) particles and any optional inorganic filler other than waste glass (e.g., sharded glass) particles to form an (unhardened) synthetic stone mixture. The amount of waste glass (e.g., sharded glass) particles is optionally 1 to 90% by weight, or 1 to 70% by weight, or 1 to 50% by weight, or 1 to 30% by weight of the synthetic stone mixture. The amount of waste glass (e.g., sharded glass) particles in the synthetic stone mixture relative to the weight of the synthetic stone is at least 2% by weight, or at least 4% by weight, or at least 10% by weight, and / or at most 90% by weight, or at most 70% by weight, or at most 50% by weight, or at most 30% by weight. The sum of the weights of the waste glass (e.g., sharded glass) particles and / or optional inorganic fillers (different from waste glass (e.g., sharded glass) particles) is optionally at least 70% by weight, or at least 80% by weight, or at least 85% by weight of the synthetic stone mixture. Optionally, the amount of hardenable adhesive in the synthetic stone mixture ranges from 5 to 30% by weight, or 5 to 15% by weight.

[0103] Mixing can be achieved using methods such as stirring with conventional mixers known in the art. The curable binder can be an organic resin, which, upon curing, enhances the cohesive and adhesive forces between inorganic fillers in the synthetic stone mixture. These organic resins are preferably thermosetting liquid resins, such as unsaturated polyester resins, methacrylate resins, vinyl resins, and epoxy resins. These resins are preferably reactive resins and harden during curing or crosslinking reactions.

[0104] In addition, additives may be added during this mixing step, selected from pigments, curing catalysts, curing accelerators, UV stabilizers, or mixtures thereof. Optional inorganic fillers (different from waste glass (e.g., shattered glass)) may be selected from stone, stone-like materials, or ceramic materials, recycled silicate glass particles, silicate frit particles, ceramic particles, or mixtures thereof. These fillers can be added to the synthetic stone mixture in different particle sizes and can be obtained by crushing and / or grinding natural or artificial materials. These inorganic fillers can be sourced from specialized companies that sell them in dry condition and classify them according to their particle size.

[0105] Other inorganic fillers (different from waste glass (e.g., broken glass) particles) may be in granular form, preferably with a particle size range of 2.0 to 0.063 mm (fine particles), or a particle size range of less than 63 micrometers (micro powder). For fine particles of inorganic fillers, the particle size range may be 1.2 to 0.1 mm, 0.7 to 0.3 mm, 0.4 to 0.1 mm, or 0.3 to 0.063 mm. These inorganic fillers (different from waste glass (e.g., broken glass) particles) are preferably selected from recycled silicate glass particles, silicate frit particles, ceramic particles, or mixtures thereof. The oxide composition of the inorganic fillers (different from waste glass (e.g., broken glass)) may differ from the composition of the waste glass (e.g., broken glass) particles of the present invention.

[0106] Uncured synthetic stone mixtures may contain other additives, such as colorants or pigments, accelerators or catalysts for resin curing or hardening (e.g., free radical initiators), and facilitators for bonding between fillers and resin (e.g., silanes). The types of these additives and their proportions are known in the prior art. Optionally, the amount of these additives in the synthetic stone mixture may be from 0.01 to 5.0% by weight of the mixture.

[0107] Uncured synthetic stone mixture can be conveyed to a dispenser via a dispensing device. Suitable dispensing devices are known, such as those for dispensing (uncured) synthetic stone mixtures during the production of quartz-containing synthetic stone. The (uncured) synthetic stone mixture can optionally be moved along the length of a temporary mold. The simplest mold can be a sheet of paper or plastic. Alternatively, the mold can be a more complex elastomeric tray. The dispensing device may include a hopper with a top opening for receiving the mixture; and a conveyor belt located below the bottom outlet opening of the hopper for collecting or removing the mixture from the hopper and depositing it onto or into the mold (depending on whether the mold is sheet-like or tray-like). Other dispensing devices and molds may also be used within the general concept of this disclosure.

[0108] The uncured synthetic stone mixture dispensed into the mold can be covered with a protective sheet on its top surface and then subjected to vacuum vibratory compaction. In one example, the mixture is fed into the compaction zone of a press and inserted into a sealed chamber. The chamber is then sealed, and a suitable vacuum pump is used to create a vacuum. Once the desired vacuum level is reached (e.g., 5 to 40 mbar), the press's piston rod applies compaction pressure while the piston vibrates vertically (e.g., at a frequency of 2,000 to 4,000 Hz). During vacuum vibratory compaction, trapped air in the synthetic stone mixture is essentially expelled.

[0109] The compacted mixture then enters the hardening or curing stage. In this stage, depending on the resin type and whether a suitable catalyst or accelerator is used, the mixture is placed in a curing oven for temperature treatment, appropriately heated to a temperature between 80 and 120°C, with a residence time in the oven typically between 20 and 60 minutes. After curing, the hardened compacted mixture is cooled to 40°C or below.

[0110] After hardening, the resulting hardened synthetic stone can be made into blocks, slabs, sheets or flats, and can be cut and / or calibrated to the required final size, and can be finished (polished or ground) on one or two of its larger surfaces, depending on the intended use.

[0111] This disclosure covers all possible combinations of the implementation methods and aspects disclosed herein.

[0112] experiment

[0113] Definition and testing methods: XRF: Commercial XRF spectrometers can be used to analyze the oxides of particles using X-ray fluorescence spectroscopy.

[0114] For example, approximately 1 g of sample disc is mixed with lithium tetraborate and calcined in air at 1050°C for 25 minutes under normal pressure, followed by spectroscopic analysis. Results are expressed as the relative weight percentage of oxides (such as SiO2, Al2O3, etc. listed in the table) in the post-calcination chemical composition, excluding any "loss on ignition" components (e.g., volatile substances or organic matter that evaporate or decompose during calcination). The spectrometer must be pre-calibrated using multi-point calibration curves with known concentrations of standards. XRF analysis can be performed according to international standard ISO 12677:2011.

[0115] XRD: Powder X-ray diffraction (XRD) using MoKα1 radiation (0.7093 Å) with a commercially available instrument (e.g., the Bruker D8 Advance) for 4 hours at a temperature range of 2°C to 35°C allows for the identification and quantification of crystalline phases within particles. After obtaining the X-ray diffraction data, quantitative analysis is performed using the Rietveld method. The content of the crystalline silica phase is calculated as a weight percentage of the analyzed sample. Most commercially available XRD instruments have an accuracy of approximately 1% by weight, but some offer higher accuracy.

[0116] Particle size analysis: Particle size (also known as particle diameter) can be measured by sieving using sieves of different mesh sizes. For waste glass particles (e.g., broken glass) with a particle size less than 200 micrometers, their particle size distribution can be measured by laser diffraction using commercially available equipment (e.g., the Malvern Panalytical Mastersizer 3000 equipped with a hydraulic tank). During measurement, the particle sample can be dispersed in deionized water using an ultrasonic probe. The laser diffractometer provides particle size distribution curves (particle volume vs. particle size) and the D10, D50, and D90 statistical values ​​of the particle population (corresponding to the particle size values ​​of 10%, 50%, or 90% of the sample particle population, respectively).

[0117] Colorimetric method: The colorimetric properties and transparency of particles in a polymer matrix can be measured from a disc prepared as follows: 50 g of particles are mixed with 50 g of commercially available unsaturated polyester resin, and 0.75 g of organic MEKP peroxide and 0.12 g of cobalt octanoate (6% cobalt) are added as catalysts. After thorough mixing, the mixture is poured into an aluminum mold to a thickness of 5 mm. The mixture is then cured at 70°C for 20 minutes, followed by standing for 30 to 40 minutes to reach room temperature. After removing the aluminum mold, the colorimetric properties and transparency of the resulting disc are measured. The colorimetric properties can be measured using a commercially available spectrophotometer (e.g., Konica Minolta CM-3600d) and expressed in L... a b Coordinate values ​​(CIELAB color space) are used to represent L, where L Indicates brightness, from black (0) to white (100); a Indicates a range from green (-) to red (+); b This indicates a range from blue (-) to yellow (+).

[0118] Embodiments of the present invention

[0119] To form synthetic stone containing waste glass, waste glass based on one or more of the following is provided: i. Container glass and / or cutlery glass (from recycled container glass); ii. Float glass (from recycled window glass and flat glass); iii. Pharmaceutical (medical) glass (borosilicate glass derived from recycled pharmaceutical glass); iv. Photovoltaic (PV) glass (from recycled photovoltaic glass); v. Insulating glass (e.g., glass wool) (from recycled insulating glass wool); vi. Reinforcing glass fibers (from recycled composite materials or other sources of waste glass fibers); and / or vii. LCD glass (from recycled LCD screens).

[0120] 12 g of each type of waste glass was placed in separate beakers, and 8 g of epoxy resin (Fugante™ Epoxy 2k) was added to each beaker. The mixtures were mixed in a HausChild high-speed mixer at 3000 rpm for 60 seconds. The mixtures were then poured into individual alumina cups for curing. To harden the samples, they were placed at 35°C and atmospheric pressure for 24 hours. The colorimetric properties of the samples were measured after curing.

[0121] In these non-limiting embodiments, the resin combined with waste glass (e.g., shattered glass) is Fugante™ Epoxy 2k, an epoxy resin. Alternatively, the resin can be other epoxy resins, polyester resins, or polyurethane resins. Non-limiting examples of polyester resins include AROPOL™ LP 67400 (manufactured by INEOS™), phthalic acid type (manufactured by Ashland™), dicyclopentadiene type (manufactured by Ashland™), isophthalic acid type (manufactured by Ashland™), and POLARIS (manufactured by Ashland™). Non-limiting examples of polyurethane resins include URETAN NR (manufactured by Cores™) or PUCORE NG (manufactured by Cores™). When using mineral fillers and resins to form synthetic stone (e.g., for kitchen countertops, exterior walls, bathrooms, or furniture), the amount of mineral filler is typically 80 to 92% by weight, and the amount of resin (optionally resins of the aforementioned types) is 8 to 20% by weight.

[0122] Samples were formed as described above (different options for waste glass are i, ii, iii, iv, v, vi to vii), and then colorimetric measurements were performed. Due to the high transparency of glass, an opacity chart was used as a background to measure the chromaticity coordinates; this chart is also known as Leneta™ paper (commonly used in the paint industry). This paper has two sides with two different standard colors (black and white). First, the sample was measured using the white background of the Leneta™ paper, and then the sample was measured using the black background of the Leneta™ paper. The chromaticity coordinates were measured using a Konica Minolta CM-3600d and in L... a b Coordinate values ​​(CIELAB color space) are used to represent the sample. A disc photograph is taken by placing the sample between the white and black sides.

[0123] Table 1 lists the colorimetric results obtained from the example synthetic stone samples: Table 1: Colorimetric Results

[0124] in conclusion

[0125] The inventors have demonstrated that waste glass (e.g., shattered glass) can be combined with adhesives to form synthetic stone. Synthetic stone formed from these components possesses similar physical characteristics to synthetic stone formed from a combination of quartz and / or cristobalite with adhesives, without the disadvantage of potentially harmful dust formation that can result from processing synthetic stone. Furthermore, the addition of waste glass (e.g., shattered glass) provides synthetic stone manufacturers with a wider range of color options, making it possible to add unique colors to synthetic stone.

[0126] The use of recycled glass in synthetic stone offers at least the following benefits: - Reduce the total carbon footprint of synthetic stone (compared to using new, non-recycled materials).

[0127] - Reduce the total content of crystalline silica.

[0128] - Maintain the high transparency of synthetic stone, thus preserving its aesthetic appeal.

[0129] According to the present invention, the waste glass contained in the synthetic stone: - It can be white or near-white, and can be transparent or semi-transparent.

[0130] - It can have good chemical resistance.

[0131] - It can have a suitable porosity of less than or equal to 6%.

[0132] In this specification and claims, "comprising" and its variations mean including the specified features, steps, or integers. These terms should not be construed as excluding the presence of other features, steps, or components.

[0133] The features disclosed in the foregoing specification, claims or drawings, whether in their specific form, or as means for performing the disclosed functions, or as methods or processes for obtaining the disclosed results (as the case may be), can be used alone or in any combination to implement the invention in various forms.

Claims

1. A synthetic stone comprising: Waste glass, and Adhesive.

2. The synthetic stone according to claim 1, wherein the waste glass is broken glass.

3. The synthetic stone according to claim 1 or 2, wherein the waste glass comprises or is composed of the following substances: i. Container glass with the following chemical composition: and / or; ii. Float glass with the following chemical composition: and / or; iii. Pharmaceutical (medical) glass having the following chemical composition: And / or, iv. Photovoltaic (PV) glass with the following chemical composition: And / or, v. Insulating glass (e.g., glass wool) having the following chemical composition: And / or, vi. Low-alkali glass fibers with the following chemical composition: And / or, vii. Borosilicate glass fibers with the following chemical composition: And / or, viii. LCD glass with the following chemical composition: UI refers to unavoidable impurities.

4. The synthetic stone according to any one of claims 1 to 3, wherein the synthetic stone comprises: 1 to 90% by weight, or 1 to 70% by weight, or 1 to 40% by weight, or 1 to 30% by weight of waste glass; or, 2 to 90% by weight, or 2 to 70% by weight, or 2 to 40% by weight, or 2 to 30% by weight of waste glass; or, 5 to 90% by weight, or 5 to 70% by weight, or 5 to 40% by weight, or 5 to 30% by weight of waste glass.

5. The synthetic stone according to any one of claims 1 to 4, wherein the waste glass is in granular form; optionally, wherein the granules: The particle size ranges from 1.0 to 0.063 mm (fine particles), or the particle size is less than 63 micrometers (micro powder); and / or, The particle size D90 is less than 50 micrometers, or less than 40 micrometers, or between 10 and 40 micrometers.

6. The synthetic stone according to any one of claims 1 to 5, wherein the adhesive comprises or is composed of resin; optionally, wherein the synthetic stone comprises 6 to 20% by weight of resin; optionally, The resin is an epoxy resin, a polyester resin, or a polyurethane resin; optionally, the resin is a 2K epoxy resin.

7. The synthetic stone according to any one of claims 1 to 6, wherein the synthetic stone further comprises pigment, silane, catalyst, accelerator or a mixture of any two, three or four of these components.

8. The synthetic stone according to any one of claims 1 to 7, wherein the synthetic stone comprises: Less than 1% by weight of crystalline SiO2, or less than 0.5% by weight of crystalline SiO2, or less than 0.1% by weight of crystalline SiO2, or no crystalline SiO2; and / or, Less than 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight, or less than 0.01% by weight of cristobalite, quartz, or cristobalite and quartz; and / or, Trace amounts (less than 1% by weight, or less than 0.5% by weight, or less than 0.01% by weight) of wollastonite, diopside, calcium magnesium silicate, mica and / or sphene.

9. The synthetic stone according to any one of claims 1 to 8, wherein the waste glass: a. White or near-white; b. Transparent or semi-transparent; c. For chemical resistance; and / or, d. Has an open area ratio of less than or equal to 6%.

10. A coating composition; Or, an ink composition; Or, a filter medium; Or, a ceramic composition; Alternatively, a dental composition; or a biomedical composition; Or, an implantable material; Or, a type of fuel cell; Or, a nuclear waste solidification composition comprising the synthetic stone according to any one of claims 1 to 9.

11. A method for forming synthetic stone, optionally the synthetic stone according to any one of claims 1 to 9, the method comprising the following steps: Provide waste glass; Mix waste glass with adhesive, and The mixture is hardened to form synthetic stone.

12. The method of claim 11, wherein the method further comprises: In the mixing step, pigments are added to obtain the desired color of the synthetic stone; And / or, In the mixing step, one or more components selected from a list consisting of pigments, silanes, catalysts, accelerators, or mixtures of any two, three, or four of these components are added.

13. The method according to claim 11 or 12, wherein: The waste glass is as described in any one of claims 2, 3, or 9; and / or, The adhesive is as described in claim 6.

14. Use of waste glass combined with adhesives in the production of synthetic stone; optionally, said synthetic stone as described in any one of claims 1 to 9.

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